1

Supporting Information

In situ transformation of a tridentate to a tetradentate unsymmetric Schiff base ligand via

deaminative coupling in Ni(II) complexes crystal structures magnetic properties and catecholase

activity study

Monotosh Mondalab Soumavo Ghosha Souvik Maitya Sanjib Giric Ashutosh Ghoshaa Department of Chemistry University College of Science University of Calcutta 92 APC Road

Kolkata-700 009 India b Department of Chemistry Haldia Government college Debhog Purba Medinipur-721657 Indiac Department of Chemistry Sri Ramkrishna Sarada Vidya Mahapitha Kamarpukur West Bengal 712612

India

E-mail ghosh_59yahoocom Fax +91-33-2351-9755 Tel +91-94-3334-4484

Table of contents

Serial

No

Contents FigTable

No

Page No

1 ESI-MS spectra of 1-3 in methanol Fig S1-S3 3-4

2 ESI-MS spectrum of reaction mixture from which metal

complex 2 is isolated after one week in methanol

Fig S4 4

3 ESI-MS spectrum of reaction mixture in methanol taken

immediately after mixing in situ generated 1 and

NH4SCN in 12 molar ratios

Fig S5 5

4 ESI-MS spectrum of the 11 molar mixture of 1 and

purified nickel perchlorate complex of the unreduced

ligand taken after one week in methanol

Fig S6 5

5 ESI-MS spectrum of the 114 molar mixture of 1

purified nickel perchlorate complex of the unreduced

ligand and NH4SCN taken after one week in methanol

Fig S7 6

Electronic Supplementary Material (ESI) for Inorganic Chemistry FrontiersThis journal is copy the Partner Organisations 2019

2

6 ESI-MS spectrum of the 12 molar mixture of 1 and

NH4SCN taken after one week in methanol

Fig S8 6-7

7 Increase in absorbance around 401 nm after addition of

equal volumes 110-2(M) of 35-DTBC to a 110minus4 M

methanol solution of 1 The spectra were recorded in

every 5 min interval

Fig S9 7

8 Plot of the initial rates vs substrate concentration for the

oxidation of 35-DTBC catalyzed by 1 The inset shows

LineweaverndashBurk plot

Fig S10 7

9 Proposed mechanism for catalytic oxidation of 35-

DTBC to 35-DTBQ by 1

Fig S11 8

10 ESI-MS spectra of 1 and 3 with 35-DTBC in methanol Fig S12-S13 9

11 Field dependent molar magnetization for 1 and 3 Fig S14 10

12 Plot of experimental J values in cm-1 with Ni-

O(phenoxido)-Ni angles

Fig S15 10

13 Selected distances (Aring) and angles (deg) for 1ndash3 Table S1-S3 10-13

14 Different concentrations of substrate (35-DTBC) in

methanol for kinetic measurement

Table S4 14

15 Kinetic parameters for the oxidation of 35-DTBC

catalyzed by 1 and 3 in methanol

Table S5 14

16 Experimental J value vs angNindashOndashNi angle for earlier

reported diphenoxido bridged dinuclear NiII complexes

Table S6 14-15

17 Selected Ni(II) complexes showing catecholase activity

with Kcat values

Table S7 15-16

3

Fig S1 ESI-MS spectrum of 1 in methanol

Fig S2 ESI-MS spectrum of 2 in methanol

4

Fig S3 ESI-MS spectrum of 3 in methanol

Fig S4 ESI-MS spectrum of reaction mixture from which metal complex 2 is isolated after one week in methanol

5

Fig S5 ESI-MS spectrum of reaction mixture in methanol taken immediately after mixing in situ generated 1 and NH4SCN in 12 ratios

Fig S6 ESI-MS spectrum of the 11 molar mixture of 1 and purified nickel perchlorate complex of the unreduced ligand taken after one week in methanol

6

Fig S7 ESI-MS spectrum of the 114 molar mixture of 1 purified nickel perchlorate complex of the unreduced ligand and NH4SCN taken after one week in methanol

7

Fig S8 ESI-MS spectrum of the 12 molar mixture of 1 and NH4SCN taken after one week in methanol

Fig S9 Increase in absorbance around 401 nm after addition of equal volumes 110-2(M) of 35-DTBC to a 110minus4 M methanol solution of 1 The spectra were recorded in every 5 min interval

Fig S10 Plot of the initial rates vs substrate concentration for the oxidation of 35-DTBC catalyzed by 1 The inset shows LineweaverndashBurk plot

8

Fig S11 Proposed mechanism for catalytic oxidation of 35-DTBC to 35-DTBQ by 1

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

2

6 ESI-MS spectrum of the 12 molar mixture of 1 and

NH4SCN taken after one week in methanol

Fig S8 6-7

7 Increase in absorbance around 401 nm after addition of

equal volumes 110-2(M) of 35-DTBC to a 110minus4 M

methanol solution of 1 The spectra were recorded in

every 5 min interval

Fig S9 7

8 Plot of the initial rates vs substrate concentration for the

oxidation of 35-DTBC catalyzed by 1 The inset shows

LineweaverndashBurk plot

Fig S10 7

9 Proposed mechanism for catalytic oxidation of 35-

DTBC to 35-DTBQ by 1

Fig S11 8

10 ESI-MS spectra of 1 and 3 with 35-DTBC in methanol Fig S12-S13 9

11 Field dependent molar magnetization for 1 and 3 Fig S14 10

12 Plot of experimental J values in cm-1 with Ni-

O(phenoxido)-Ni angles

Fig S15 10

13 Selected distances (Aring) and angles (deg) for 1ndash3 Table S1-S3 10-13

14 Different concentrations of substrate (35-DTBC) in

methanol for kinetic measurement

Table S4 14

15 Kinetic parameters for the oxidation of 35-DTBC

catalyzed by 1 and 3 in methanol

Table S5 14

16 Experimental J value vs angNindashOndashNi angle for earlier

reported diphenoxido bridged dinuclear NiII complexes

Table S6 14-15

17 Selected Ni(II) complexes showing catecholase activity

with Kcat values

Table S7 15-16

3

Fig S1 ESI-MS spectrum of 1 in methanol

Fig S2 ESI-MS spectrum of 2 in methanol

4

Fig S3 ESI-MS spectrum of 3 in methanol

Fig S4 ESI-MS spectrum of reaction mixture from which metal complex 2 is isolated after one week in methanol

5

Fig S5 ESI-MS spectrum of reaction mixture in methanol taken immediately after mixing in situ generated 1 and NH4SCN in 12 ratios

Fig S6 ESI-MS spectrum of the 11 molar mixture of 1 and purified nickel perchlorate complex of the unreduced ligand taken after one week in methanol

6

Fig S7 ESI-MS spectrum of the 114 molar mixture of 1 purified nickel perchlorate complex of the unreduced ligand and NH4SCN taken after one week in methanol

7

Fig S8 ESI-MS spectrum of the 12 molar mixture of 1 and NH4SCN taken after one week in methanol

Fig S9 Increase in absorbance around 401 nm after addition of equal volumes 110-2(M) of 35-DTBC to a 110minus4 M methanol solution of 1 The spectra were recorded in every 5 min interval

Fig S10 Plot of the initial rates vs substrate concentration for the oxidation of 35-DTBC catalyzed by 1 The inset shows LineweaverndashBurk plot

8

Fig S11 Proposed mechanism for catalytic oxidation of 35-DTBC to 35-DTBQ by 1

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

3

Fig S1 ESI-MS spectrum of 1 in methanol

Fig S2 ESI-MS spectrum of 2 in methanol

4

Fig S3 ESI-MS spectrum of 3 in methanol

Fig S4 ESI-MS spectrum of reaction mixture from which metal complex 2 is isolated after one week in methanol

5

Fig S5 ESI-MS spectrum of reaction mixture in methanol taken immediately after mixing in situ generated 1 and NH4SCN in 12 ratios

Fig S6 ESI-MS spectrum of the 11 molar mixture of 1 and purified nickel perchlorate complex of the unreduced ligand taken after one week in methanol

6

Fig S7 ESI-MS spectrum of the 114 molar mixture of 1 purified nickel perchlorate complex of the unreduced ligand and NH4SCN taken after one week in methanol

7

Fig S8 ESI-MS spectrum of the 12 molar mixture of 1 and NH4SCN taken after one week in methanol

Fig S9 Increase in absorbance around 401 nm after addition of equal volumes 110-2(M) of 35-DTBC to a 110minus4 M methanol solution of 1 The spectra were recorded in every 5 min interval

Fig S10 Plot of the initial rates vs substrate concentration for the oxidation of 35-DTBC catalyzed by 1 The inset shows LineweaverndashBurk plot

8

Fig S11 Proposed mechanism for catalytic oxidation of 35-DTBC to 35-DTBQ by 1

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

4

Fig S3 ESI-MS spectrum of 3 in methanol

Fig S4 ESI-MS spectrum of reaction mixture from which metal complex 2 is isolated after one week in methanol

5

Fig S5 ESI-MS spectrum of reaction mixture in methanol taken immediately after mixing in situ generated 1 and NH4SCN in 12 ratios

Fig S6 ESI-MS spectrum of the 11 molar mixture of 1 and purified nickel perchlorate complex of the unreduced ligand taken after one week in methanol

6

Fig S7 ESI-MS spectrum of the 114 molar mixture of 1 purified nickel perchlorate complex of the unreduced ligand and NH4SCN taken after one week in methanol

7

Fig S8 ESI-MS spectrum of the 12 molar mixture of 1 and NH4SCN taken after one week in methanol

Fig S9 Increase in absorbance around 401 nm after addition of equal volumes 110-2(M) of 35-DTBC to a 110minus4 M methanol solution of 1 The spectra were recorded in every 5 min interval

Fig S10 Plot of the initial rates vs substrate concentration for the oxidation of 35-DTBC catalyzed by 1 The inset shows LineweaverndashBurk plot

8

Fig S11 Proposed mechanism for catalytic oxidation of 35-DTBC to 35-DTBQ by 1

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

5

Fig S5 ESI-MS spectrum of reaction mixture in methanol taken immediately after mixing in situ generated 1 and NH4SCN in 12 ratios

Fig S6 ESI-MS spectrum of the 11 molar mixture of 1 and purified nickel perchlorate complex of the unreduced ligand taken after one week in methanol

6

Fig S7 ESI-MS spectrum of the 114 molar mixture of 1 purified nickel perchlorate complex of the unreduced ligand and NH4SCN taken after one week in methanol

7

Fig S8 ESI-MS spectrum of the 12 molar mixture of 1 and NH4SCN taken after one week in methanol

Fig S9 Increase in absorbance around 401 nm after addition of equal volumes 110-2(M) of 35-DTBC to a 110minus4 M methanol solution of 1 The spectra were recorded in every 5 min interval

Fig S10 Plot of the initial rates vs substrate concentration for the oxidation of 35-DTBC catalyzed by 1 The inset shows LineweaverndashBurk plot

8

Fig S11 Proposed mechanism for catalytic oxidation of 35-DTBC to 35-DTBQ by 1

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

6

Fig S7 ESI-MS spectrum of the 114 molar mixture of 1 purified nickel perchlorate complex of the unreduced ligand and NH4SCN taken after one week in methanol

7

Fig S8 ESI-MS spectrum of the 12 molar mixture of 1 and NH4SCN taken after one week in methanol

Fig S9 Increase in absorbance around 401 nm after addition of equal volumes 110-2(M) of 35-DTBC to a 110minus4 M methanol solution of 1 The spectra were recorded in every 5 min interval

Fig S10 Plot of the initial rates vs substrate concentration for the oxidation of 35-DTBC catalyzed by 1 The inset shows LineweaverndashBurk plot

8

Fig S11 Proposed mechanism for catalytic oxidation of 35-DTBC to 35-DTBQ by 1

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

7

Fig S8 ESI-MS spectrum of the 12 molar mixture of 1 and NH4SCN taken after one week in methanol

Fig S9 Increase in absorbance around 401 nm after addition of equal volumes 110-2(M) of 35-DTBC to a 110minus4 M methanol solution of 1 The spectra were recorded in every 5 min interval

Fig S10 Plot of the initial rates vs substrate concentration for the oxidation of 35-DTBC catalyzed by 1 The inset shows LineweaverndashBurk plot

8

Fig S11 Proposed mechanism for catalytic oxidation of 35-DTBC to 35-DTBQ by 1

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

8

Fig S11 Proposed mechanism for catalytic oxidation of 35-DTBC to 35-DTBQ by 1

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

9

Fig S12 ESI-MS spectrum of 1 with 35-DTBC in methanol

Fig S13 ESI-MS spectrum of 3 with 35-DTBC in methanol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

10

Fig S14 Field dependent molar magnetization for 1 and 3

Fig S15 Plot of experimental J values in cm-1 with Ni-O(phenoxido)-Ni angles

Table S1 Selected bond lengths (Aring) for 1ndash3

Bonds length 1 2 3

Ni(1)minusO(10) 2060(2) 2044(4) 2100(2)

Ni(1)minusO(1) 2134(4)

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

11

Ni(1)minusO(2) 2132(3)

Ni(1)minusN(1) 2208(3) 2029(6)

Ni(1)minusO(10)a 2055(2)

Ni(1)minusN(2) 2097(4) 2155(6)

Ni(1)minusN(18) 2096(3) 2128(6) 2092(3)

Ni(1)minusN(22) 2097(3) 2117(6) 2133(3)

Ni(1)minusO(31) 2067(5) 2051(2)

Ni(2)minusO(10) 2181(2)

Ni(2)minusO(31) 2053(2)

Ni(2)minusN(1) 2063(3)

Ni(2)minusO(10)a 2181(2)

Ni(2)minusO(31)a 2053(2)

Ni(2)minusN(1)a 2063(3)a=1-x 1-y 1-z for complex 1 a= -x y 12-z for complex 3

Table S2 Selected bond angles (deg) for 1

1

O(10)Ni(1)N(1) 8840(9)

O(10)Ni(1)N(2) 10189(11)

O(10)Ni(1)O(10)a 7756(8)

O(10)Ni(1)N(18) 16726(9)

O(10)Ni(1)N(22) 9074(9)

N(1)Ni(1)N(2) 8662(12)

O(10)aNi(1)N(1) 9439(9)

N(1)Ni(1)N(18) 8563(11)

N(1)Ni(1)N(22) 17614(11)

O(10)aNi(1)N(2) 17884(11)

N(2)Ni(1)N(18) 8901(12)

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

12

N(2)Ni(1)N(22) 8988(12)

O(10)aNi(1)N(18) 9166(9)

O(10)aNi(1)N(22) 8910(9)

N(18)Ni(1)N(22) 9594(10)

Ni(1)O(10)Ni(1)a 10244(8)

a=1-x 1-y 1-z

Table S3 Selected bond angles (deg) for 2ndash3

2 3

O(1)-Ni(1)-O(2) 17110(12)

O(1)-Ni(1)-O(10) 8813(11)

O(1)-Ni(1)-O(31) 8697(12)

O(1)-Ni(1)-N(18) 9330(14)

O(1)Ni(1)N(22) 9731(13)

O(2)Ni(1)O(10) 8452(10)

O(2)Ni(1)O(31) 8697(9)

O(2)Ni(1)N(18) 9207(11)

O(2)Ni(1)N(22) 8954(11)

N(1)Ni(1)N(2) 1732(2)

N(1)Ni(1)N(18) 928(2)

N(1)Ni(1)N(22) 923(2)

N(2)Ni(1)N(18) 910(2)

N(2)Ni(1)N(22) 933(2)

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

13

O(10)Ni(1)N(1) 898(2)

O(10)Ni(1)N(2) 8449(19)

O(31)Ni(1)N(1) 921(2)

O(31)Ni(1)N(2) 838(2)

O(10)Ni(1)O(31) 8639(17) 8118(9)

O(10)Ni(1)N(18) 910(2) 9290(11)

O(10)Ni(1)N(22) 1767(2) 17245(10)

O(31)Ni(1)N(18) 1744(2) 17406(11)

O(31)Ni(1)N(22) 9096(19) 9390(11)

N(18)Ni(1)N(22) 915(2) 9195(13)

O(10)Ni(2)O(31) 7922(9)

O(10)Ni(2)N(1) 9118(11)

O(10)Ni(2)O(10)a 8727(8)

O(10)Ni(2)O(31)a 8685(9)

O(10)Ni(2)N(1)a 17760(11)

O(31)Ni(2)N(1) 9467(11)

O(10)a Ni(2)O(31) 8685(9)

O(31)Ni(2)O(31)a 16076(9)

O(31)Ni(2)N(1)a 9887(11)

O(10)aNi(2)N(1) 17760(11)

O(31)aNi(2)N(1) 9887(11)

N(1)Ni(2)N(1)a 9042(13)

O(10)aNi(2)O(31)a 7922(9)

O(10)aNi(2)N(1)a 9119(11)

O(31)aNi(2)N(1)a 9467(11)a= -x y 12-z

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

14

Table S4 Different concentrations of substrate (35-DTBC) in methanol for kinetic measurement

Metal complex and its concentration (M)

35-DTBC (M)

1(510-5) 0005 00035 00025 00015 0001 000053(510-5) 00075 00065 0005 00035 00025 00015 0001 00005

Table S5 Kinetic parameters for the oxidation of 35-DTBC catalyzed by 1 and 3 in methanol

Table S6 Experimental J value vs angNindashOndashNi angle for earlier reported diphenoxido bridged dinuclear NiII complexes

Vmax(M secminus1) Std error KM (M) Std error kcat (hminus1)

1 109times10-7 883times10-8 039times10-3 832times10-6 79

3 201times10-7 122times10-8 230times10-3 682times10-5 145

Compounds J cm-1 Ni-O-Ni angle

(deg)

References

[Ni2L12(NO2)2]middotCH2Cl2middotC2H5OH

2H2O

ndash1052 9828 45a

[Ni2L22(NO3)2] ndash2034 9931 42a

[Ni2L22(NO2)2] ndash2525 10001 42a

[Ni2(L3)2(NCS)2] minus4664 10454 26a

[Ni2(L4)2(NCS)2] minus709 10292 26a

[Ni2(L5)2(NCS)2] minus6804 10384 26a

[Ni2(L6)2(NO3)2] ndash2427 9975 38

[Ni2(L7)2(OAc)2] ndash5028 10058 45b

Ni(Hsalhyph)Cl(H2O)2 ndash1480 99 45c

[Ni2L8(H2O)4(ClO4)2 4NH2CONH2 minus34 995 45d

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

15

HL1= 2-[(3-amino-propylimino)-methyl]-phenol

HL2= 2-([3-(dimethylamino)propyl]iminomethyl)phenol

HL3= 2-[1-(3-methylamino-propylamino)-ethyl]-phenol

HL4= 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol

HL5=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol

HL6= 2-[(3-Methylamino-propylimino)-methyl]-phenol

HL7= 2-[(3-methylamino-propylimino)-methyl]-phenol)

HL9= 2-((E)-(3-aminopentylimino)methyl)phenol

HL10= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

HL11= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylimino)-methyl]-phenol

HL12= 4-bromo-2-[(2-hydroxy-11-dimethyl-ethylamino)-methyl]-phenol

Table S7 Selected Ni(II) complexes showing catecholase activity with Kcat values

Ni complexes Solvent Kcat(h-1) Ref

[Ni2(L1)(SCN)2(AcO)-(H2O)] CH3OH 8639 41

[Ni2(L2)(SCN)3(CH3OH)2] CH3OH 1611 41

[ Ni2L8(NCS)2(H2O)2] 2Me2NCHO minus426 992 45d

[Ni2L8(MeOH)2(ClO4)2]2NHEt minus59 1013 45d

[NiL92(o-HSal)]middot2H2O ndash1378 9765 45e

[Ni2L92(o-Hap)2] ndash1687 9885 45e

[Ni2L92(o-Hnap)2] ndash1014 9756 45e

[Ni2L102(CH3CN)4](ClO4)22CH3CN minus3410 10241 42c

[Ni2L102(NCS)2 (CH3CN)2] minus2372 10242 42c

[Ni2(L11)2(OAc)2(H2O)2]middotCH3CN minus1248 9974 45f

[Ni2(L12)2(SCN)2(CH3OH)2]middotCH3OH minus1487 10051 45f

[Ni2L2(CH3CN)4](ClO4)2CH3CN minus3222 10244 This work

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol

16

[Ni2(L1)(SCN)3(H2O)(CH3OH)] CH3OH 1540 41

[Ni2(L2)(SCN)(AcO)2] CH3OH 3037 41

[Ni2(L1)(N3)3(H2O)2] CH3OH 1728 41

[Ni2(L2)(N3)3(H2O)2] CH3OH 2641 41

[Ni2(L3)(AcO)2-(N(CN)2)]n CH3OH 1286 41

[Ni2(L4)(AcO)2(N(CN)2)] CH3OH 2750 41

[Ni2(L5)2(NCS)2] CH3CN 641 26a

[Ni2(L6)2(NCS)2] CH3CN 511 26a

[Ni2(L7)2(NCS)2] CH3CN 817 26a

[NiL8(H2O)3]I2middotH2O CH3OH 926 40a

[NiL8(H2O)3]Br2middotH2O CH3OH 848 40a

[Ni2(L9)2(H2O)4](NO3)2 CH3OH 474 40a

[Ni5(L10)2(OAc)6(OH)2] middot 55 H2O CH3OH 477 40a

[NiL8(H2O)3](NO3)2 CH3OH 526 40a

[NiL11(H2O)3](NO3)2 CH3OH 129 40a

[Ni4(L12)2(H2O)8(micro2H2O)2](NO3)6(H2O)6 DMF 12 39e

[Ni2L13(PhCOO)(H2O)2]ClO4 CH3OH 1674 26b

[Ni2L12(CH3CN)4](ClO4)22CH3CN

CH3OH79

Present

work

[Ni3(L2)2(NCS)2(H2O)4]H2OCH3OH

145Present

work

1 HL1=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = NN-dimethylethylene2 HL2=26-bis(R2-iminomethyl)-4-R1-phenol R1 = tert-butyl R2 = 2-(N-ethyl) pyridine3 HL3=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = NN-dimethylethylene4 HL4=26-bis(R2-iminomethyl)-4-R1-phenol R1 = methyl R2 = 2-(N-ethyl) pyridine

deen = 2-(diethylamino) ethylamine dmpn = 3-(dimethylamino)-1-propylamine and modaH = diacetyl monoxime

5 HL5=2-[1-(3-methylamino-propylamino)-ethyl]-phenol6 HL6=2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol 7 HL7=2-[1-(3-dimethylamino-propylamino)-ethyl]-phenol8 HL8 = 2-[(2-piperazin-1-ylethylimino)methyl]phenol9 HL9= 2-formyl-4-methyl-6-(1-(2-aminomethyl)piperidine)-iminomethylphenol10 HL10= 4-methyl-26-bis(1-(2-aminomethyl)piperidine)-iminomethylphenol11 HL11=2-[(2-piperazin-1-ylethylimino)methyl]-4-chlorophenol 12 HL12= 26 diformyl-4-isopropyl phenol

13 HL13= 2-[(3-methylamino-propylamino)-methyl]-4-nitrophenol