Activation of H2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)2(CO)ZnEt]+

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

doi:10.1021/jacs.6b05243

Activation of H₂ over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)₂(CO)ZnEt]⁺

Ian M. Riddlestone, Nasir A. Rajabi, John P. Lowe, Mary F. Mahon, Stuart A. Macgregor^*, Michael K. Whittlesey

^*Corresponding author for this work

School of Chemistry

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Abstract

Reaction of [Ru(IPr)₂(CO)H]BAr^F₄ with ZnEt₂ forms the heterobimetallic species [Ru(IPr)₂(CO)ZnEt]BAr^F₄ (2), which features an unsupported Ru-Zn bond. 2 reacts with H₂ to give [Ru(IPr)₂(CO)(η²-H₂)(H)₂ZnEt]BAr^F₄ (3) and [Ru(IPr)₂(CO)(H)₂ZnEt]BAr^F₄ (4). DFT calculations indicate that H₂ 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
DOIs	https://doi.org/10.1021/jacs.6b05243
Publication status	Published - 7 Sept 2016

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title = "Activation of H2 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]BArF4 with ZnEt2 forms the heterobimetallic species [Ru(IPr)2(CO)ZnEt]BArF4 (2), which features an unsupported Ru-Zn bond. 2 reacts with H2 to give [Ru(IPr)2(CO)(η2-H2)(H)2ZnEt]BArF4 (3) and [Ru(IPr)2(CO)(H)2ZnEt]BArF4 (4). DFT calculations indicate that H2 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.",

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

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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doi = "10.1021/jacs.6b05243",

language = "English",

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T1 - Activation of H2 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 A.

AU - Lowe, John P.

AU - Mahon, Mary F.

AU - Macgregor, Stuart A.

AU - Whittlesey, Michael K.

PY - 2016/9/7

Y1 - 2016/9/7

N2 - Reaction of [Ru(IPr)2(CO)H]BArF4 with ZnEt2 forms the heterobimetallic species [Ru(IPr)2(CO)ZnEt]BArF4 (2), which features an unsupported Ru-Zn bond. 2 reacts with H2 to give [Ru(IPr)2(CO)(η2-H2)(H)2ZnEt]BArF4 (3) and [Ru(IPr)2(CO)(H)2ZnEt]BArF4 (4). DFT calculations indicate that H2 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]BArF4 with ZnEt2 forms the heterobimetallic species [Ru(IPr)2(CO)ZnEt]BArF4 (2), which features an unsupported Ru-Zn bond. 2 reacts with H2 to give [Ru(IPr)2(CO)(η2-H2)(H)2ZnEt]BArF4 (3) and [Ru(IPr)2(CO)(H)2ZnEt]BArF4 (4). DFT calculations indicate that H2 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.

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IS - 35

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Activation of H₂ over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)₂(CO)ZnEt]⁺

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