Activation of H-2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)(2)(CO)ZnEt](+)

Ian M. Riddlestone; Nasir Ahmad Rajabi; John P. Lowe; Mary F. Mahon; Stuart Alan Macgregor; Michael K. Whittlesey

doi:10.1021/jacs.6b05243

Activation of H-2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)(2)(CO)ZnEt](+)

Ian M. Riddlestone, Nasir Ahmad Rajabi, John P. Lowe, Mary F. Mahon, Stuart Alan Macgregor, Michael K. Whittlesey

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Abstract

Reaction of [Ru(IPr)(2)(CO)H]BAr4F with ZnEt2 forms the heterobimetallic species [Ru(IPr)(2)(CO)-ZnEt]BAr4F (2), which features an unsupported Ru-Zn bond. 2 reacts with H-2 to give [Ru(IPr)(2)(CO)(eta(2)-H-2)-(H)(2)ZnEt]BAr4F (3) and [Ru(IPr)(2)(CO)(H)(2)ZnEt]BArP4 (4). DFT calculations indicate that H-2 activation at 2 proceeds via oxidative cleavage at Ru with concomitant hydride transfer to Zn. 2 can also activate hydridic E-H bonds (E = B, Si), and computed mechanisms for the facile H/H exchange processes observed in 3 and 4 are presented.

Original language	English
Pages (from-to)	11081-11084
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	35
Early online date	4 Aug 2016
DOIs	https://doi.org/10.1021/jacs.6b05243
Publication status	Published - 7 Sept 2016

Keywords

NICKEL-BORANE COMPLEX
CATALYTIC-HYDROGENATION
POLYHYDRIDE COMPLEXES
PLATINUM COMPLEXES
LIGAND COOPERATION
HYDRIDE COMPLEXES
ZINC
CLEAVAGE
COORDINATION
DIHYDROGEN

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This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.6b05243
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@article{f6884f7c49d64e48921dcd6195f99511,

title = "Activation of H-2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)(2)(CO)ZnEt](+)",

abstract = "Reaction of [Ru(IPr)(2)(CO)H]BAr4F with ZnEt2 forms the heterobimetallic species [Ru(IPr)(2)(CO)-ZnEt]BAr4F (2), which features an unsupported Ru-Zn bond. 2 reacts with H-2 to give [Ru(IPr)(2)(CO)(eta(2)-H-2)-(H)(2)ZnEt]BAr4F (3) and [Ru(IPr)(2)(CO)(H)(2)ZnEt]BArP4 (4). DFT calculations indicate that H-2 activation at 2 proceeds via oxidative cleavage at Ru with concomitant hydride transfer to Zn. 2 can also activate hydridic E-H bonds (E = B, Si), and computed mechanisms for the facile H/H exchange processes observed in 3 and 4 are presented.",

keywords = "NICKEL-BORANE COMPLEX, CATALYTIC-HYDROGENATION, POLYHYDRIDE COMPLEXES, PLATINUM COMPLEXES, LIGAND COOPERATION, HYDRIDE COMPLEXES, ZINC, CLEAVAGE, COORDINATION, DIHYDROGEN",

author = "Riddlestone, {Ian M.} and Rajabi, {Nasir Ahmad} and Lowe, {John P.} and Mahon, {Mary F.} and Macgregor, {Stuart Alan} and Whittlesey, {Michael K.}",

year = "2016",

month = sep,

day = "7",

doi = "10.1021/jacs.6b05243",

language = "English",

volume = "138",

pages = "11081--11084",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "35",

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T1 - Activation of H-2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)(2)(CO)ZnEt](+)

AU - Riddlestone, Ian M.

AU - Rajabi, Nasir Ahmad

AU - Lowe, John P.

AU - Mahon, Mary F.

AU - Macgregor, Stuart Alan

AU - Whittlesey, Michael K.

PY - 2016/9/7

Y1 - 2016/9/7

N2 - Reaction of [Ru(IPr)(2)(CO)H]BAr4F with ZnEt2 forms the heterobimetallic species [Ru(IPr)(2)(CO)-ZnEt]BAr4F (2), which features an unsupported Ru-Zn bond. 2 reacts with H-2 to give [Ru(IPr)(2)(CO)(eta(2)-H-2)-(H)(2)ZnEt]BAr4F (3) and [Ru(IPr)(2)(CO)(H)(2)ZnEt]BArP4 (4). DFT calculations indicate that H-2 activation at 2 proceeds via oxidative cleavage at Ru with concomitant hydride transfer to Zn. 2 can also activate hydridic E-H bonds (E = B, Si), and computed mechanisms for the facile H/H exchange processes observed in 3 and 4 are presented.

AB - Reaction of [Ru(IPr)(2)(CO)H]BAr4F with ZnEt2 forms the heterobimetallic species [Ru(IPr)(2)(CO)-ZnEt]BAr4F (2), which features an unsupported Ru-Zn bond. 2 reacts with H-2 to give [Ru(IPr)(2)(CO)(eta(2)-H-2)-(H)(2)ZnEt]BAr4F (3) and [Ru(IPr)(2)(CO)(H)(2)ZnEt]BArP4 (4). DFT calculations indicate that H-2 activation at 2 proceeds via oxidative cleavage at Ru with concomitant hydride transfer to Zn. 2 can also activate hydridic E-H bonds (E = B, Si), and computed mechanisms for the facile H/H exchange processes observed in 3 and 4 are presented.

KW - NICKEL-BORANE COMPLEX

KW - CATALYTIC-HYDROGENATION

KW - POLYHYDRIDE COMPLEXES

KW - PLATINUM COMPLEXES

KW - LIGAND COOPERATION

KW - HYDRIDE COMPLEXES

KW - ZINC

KW - CLEAVAGE

KW - COORDINATION

KW - DIHYDROGEN

U2 - 10.1021/jacs.6b05243

DO - 10.1021/jacs.6b05243

M3 - Article

C2 - 27490786

SN - 0002-7863

VL - 138

SP - 11081

EP - 11084

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 35

ER -

Activation of H-2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)(2)(CO)ZnEt](+)

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