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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
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