molecular catalysts with m/nh...

transfer hydrogenationL = NR2hydrogenation of ketonesL = PR2hydrogenolysis of epoxides and imides

RuNPh

Ph N

Ts

ClHH

Rn

RuL

N ClHH

N

RuX

H

MOLECULAR CATALYSTS WITH M/NH BIFUNCTIONAL UNITS

Nu H

: arene, Cp* ligand

N

RuX

H

Nu

H

X : N, PNu H : H2, (CH3)2CHOH, HCOOH, CH2(COOR)2

amine complexamide complex

RuCl

Cl

Rn

NH2

THIS WORK

A B A BNu H

catalyst precursor :

REPORTED EXAMPLES OF η1: η6-(AMINOARENE)Ru COMPLEXES

Kurosawa, Inorg. Chim. Acta, 2000

RuPh3P

Cl NH2

BF4

η6 −arene → η1 : η6 −L−arene

n−2

NH2 1) Birch reductionNH3Cl

EtOHreflux

2) HCl

n = 2, 3

(CH2)nNH3Cl

RuCl

Cl 2

RuCl

H2NN

SO2

PhPh

Wills, J. Am. Chem. Soc., 2004

RuCl

Cl 2

SO2

HN

Ph

NH3Cl

Ph

2-propanolreflux

N(C2H5)3

RuCl3 xH2O

n-1 n-1

η1−L → η1 : η6 −L−arene

THIS WORK : INTRAMOLECULAR ARENE DISPLACEMENT REACTION

NH2

CO2Et

RuCl

Cl 2

+

η1 −NH2 complex η1:η6−tethered complex

∆ RuCl

ClNH2

RuCl

ClNH2

EtOCO

EFFECT OF SUBSTITUENTS FOR η1: η6-(AMINOARENE)Ru COMPLEXES

chlorobenzene140 °C

RuCl

ClNH2

yield, %a

H >99m-CH3

p-CH3

R

>9962

80o-Si(CH3)3

m-Si(CH3)3

p-Si(CH3)3

88

90

[Ru] = 0.02 M. aIsolated yield.

time, h

21

20

22

2

18

m,p-(CH3)2 6717

RuCl

ClNH2

EtOCOR R

EFFECT OF STRUCTURE OF AMINOARENES

H 94m-Si(CH3)3

p-Si(CH3)3 56

1622

NH2R

OY

R

yield, %aR

p-Si(CH3)3

p-Si(CH3)3

time, h

21

Y

CO

69

<1<1

CH2

NH2

NH2

R1 R2

yield, %aR time, hyield, %aR1 time, hR2

CH3

CO2CH3

1813H

9898

CH3

[Ru] = 0.02 M. aIsolated yield.

RuCl N

H2

(CH3)3Si+

1H NMR

ESI-TOF

TMS

η6-C6H4 Si(CH3)3

RuCl

ClNH2

(CH3)3Si

CHCl3

SPECTRAL DATA

SYNTHESIS OF CATIONIC ARENE−Ru COMPLEXES

BF4

RuPh3P

Cl

(CH2)2NH3Cl

methanolreflux, 20 h56% yield

RuCl

ClNH2 Cl

methanolrt, 15 h42% yield

this work

RuPh3P

ClNH2

+ +PPh3 + AgBF4 NaOH + NaBF4

Kurosawa, Inorg. Chim. Acta, 2000

Ru−C(1) 2.152(9) Ru−C(2) 2.221(9) Ru−C(3) 2.276(8) Ru−C(4) 2.241(7) Ru−C(5) 2.197(6) Ru−C(6) 2.174(7) Ru−Cl 2.404(2) Ru−N 2.157(7) Ru−P 2.360(2)P−Ru−Cl 87.90(7)P−Ru−N 92.0(2)N−Ru−Cl 84.8(2)

Selected bond lengths[Å] and angles[°]

STEREOSELECTIVE FORMATION OF PHOSPHINE COMPLEXES

methanolreflux, 18 h

PPh3AgSbF6

RuCl

ClNH2

(CH3)3Si

RuCl

PPh3

NH2

SbF6(CH3)3Si

anti 70% yield

phosphine complex with ethylene tether

single diastereomer (31P NMR)

+

R1 (I > 2σ) = 0.094wR2 = 0.175P-1 (#2)Z = 2

Ru−C(1) 2.211(4) Ru−C(2) 2.255(4) Ru−C(3) 2.267(5) Ru−C(4) 2.217(5) Ru−C(5) 2.186(6) Ru−C(6) 2.222(6) Ru−Cl 2.3969(13) Ru−N 2.135(4) Ru−P 2.3541(12)

Selected bond lengths[Å] and angles[°]

P−Ru−Cl 86.13(4)P−Ru−N 90.93(13)N−Ru−Cl 81.05(13)

CH2Cl2rt, 24 h

RuCl

PPh3

NH2

(CH3)3Si SbF6

RuCl

ClNH2

(CH3)3Si

anti 52% yieldsingle diastereomer (31P NMR)

phosphine complex with propylene tether

PPh3AgSbF6

+

R1 (I > 2σ) = 0.053wR2 = 0.143P-1 (#2)Z = 4

SYNTHESIS OF CATIONIC ISOCYANIDE COMPLEX

RuCl

Cl

NH2

(CH3)3Si

RuCl

CNt-C4H9

NH2

(CH3)3Si

+ +

SbF6

CH2Cl2, rt2 h, 88% yield

IR νN≡C 2201 cm-1

AgSbF6 t-C4H9NC

RuCl

CNt-C4H9

NH2

(CH3)3SiSbF6


+ +CH2Cl2, rt2 h, 49% yield

AgSbF6 t-C4H9NCRuClCl

NH2

(CH3)3Si

Ru−Cl 2.3911(13) Ru−N(1) 2.142(3) Ru−C(13) 1.989(4) N(2)−C(13) 1.142(5)

C(13)−Ru−Cl 83.34(13)C(13)−Ru−N 86.91(12)N−Ru−Cl 81.62(11)

Selected bond lengths[Å]and angles[°]

t-C4H9NCAgSbF6

CH2Cl2rt, 1 h

Rut-C4H9NC

ClNH2

(CH3)3Si SbF6

RuCl

ClNH2

(CH3)3Si

RuCl

CNt-C4H9

NH2

(CH3)3Si SbF6

syn 16% yield anti

isocyanide complex with propylene tether

+


R1 (I > 2σ) = 0.044wR2 = 0.090P-1 (#2)Z = 2

Si(CH3)3

RuCl

Cl 2 R1 = n-C6H13

7 9aDetermined by 1H NMR.

yield, %a

EFFECT OF AMINO-TETHER IN HYDROGEN TRANSFER

O Ru catt-C4H9OK

OH

H2-propanol30 °C, 1 h

ketone:Ru:t-C4H9OK = 10:1:1, [ketone] = 0.1 M

RuCl

ClNH2

(CH3)3Si

RuCl

ClNH2

(CH3)3Si

28 >99yield, %a

RuCl

ClNH2

(CH3)3Si

<1 (without base)

RuCl

ClNR1H2

(CH3)3Si

aDetermined by 1H NMR.

HYDROGEN TRANSFER USING CATIONIC COMPLEXES

O Ru catt-C4H9OK

OH

H2-propanol30 °C, 1 h

ketone:Ru:t-C4H9OK = 10:1:1, [ketone] = 0.1 M

RuCl

PPh3

NH2

(CH3)3Si

>99 10yield, %a <1

RuCl

ClNH2

(CH3)3SiSbF6

RuCl

CNt-C4H9

NH2

(CH3)3SiSbF6

PROPOSED MECHANISM

RuCl

ClNH2

baseRu

Cl NH

RuCl

LNH2

baseRu

Cl NH

SbF6

L

RuCl

HNH2

R

OH

R

O

H

+ +

– HSbF6

– HCl

– LL

SUMMARY

Novel synthetic method for various η1:η6-(aminoarene)Ru complexes

Stereocontrol based on a planar chirality

η1 −NH2 complex η1:η6−tethered complex

∆Ru

ClCl

NH2

Potent hydrogen transfer ability

RuCl

ClNH2

EtOCO

molecular catalysts with m/nh...

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