Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium–Indium Bonds

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

doi:10.1002/chem.201705796

Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium–Indium Bonds

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

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The hydride complex [Ru(IPr)₂(CO)H][BAr^F₄], 1, reacts with InMe₃ with loss of CH₄ to form [Ru(IPr)₂(CO)(InMe)(Me)][BAr^F₄], 4, featuring an unsupported Ru−In bond with unsaturated Ru and In centres. 4 reacts with H₂ to give [Ru(IPr)₂(CO)(η²-H₂)(InMe)(H)][BAr^F₄], 5, while CO induces formation of the indyl complex [Ru(IPr)₂(CO)₃(InMe₂)][BAr^F₄], 7. These observations highlight the ability of Me to shuttle between Ru and In centres and are supported by DFT calculations on the mechanism of formation of 4 and its reactions with H₂ and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe₃ also involves CH₄ loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η⁶ interaction of one aryl substituent with Ru.

Original language	English
Pages (from-to)	1732-1738
Number of pages	7
Journal	Chemistry - A European Journal
Volume	24
Issue number	7
DOIs	https://doi.org/10.1002/chem.201705796
Publication status	Published - 1 Feb 2018

Keywords

density functional calculations
gallium
heterometallic complexes
indium
ruthenium

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@article{a19a8f2c352d4635bd746f83e2dc8f0e,

title = "Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium–Indium Bonds",

abstract = "The hydride complex [Ru(IPr)2(CO)H][BArF4], 1, reacts with InMe3 with loss of CH4 to form [Ru(IPr)2(CO)(InMe)(Me)][BArF4], 4, featuring an unsupported Ru−In bond with unsaturated Ru and In centres. 4 reacts with H2 to give [Ru(IPr)2(CO)(η2-H2)(InMe)(H)][BArF4], 5, while CO induces formation of the indyl complex [Ru(IPr)2(CO)3(InMe2)][BArF4], 7. These observations highlight the ability of Me to shuttle between Ru and In centres and are supported by DFT calculations on the mechanism of formation of 4 and its reactions with H2 and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe3 also involves CH4 loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η6 interaction of one aryl substituent with Ru.",

keywords = "density functional calculations, gallium, heterometallic complexes, indium, ruthenium",

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

note = "Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2018",

month = feb,

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doi = "10.1002/chem.201705796",

language = "English",

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AU - Riddlestone, Ian M.

AU - Rajabi, Nasir A.

AU - Macgregor, Stuart A.

AU - Mahon, Mary F.

AU - Whittlesey, Michael K.

PY - 2018/2/1

Y1 - 2018/2/1

N2 - The hydride complex [Ru(IPr)2(CO)H][BArF4], 1, reacts with InMe3 with loss of CH4 to form [Ru(IPr)2(CO)(InMe)(Me)][BArF4], 4, featuring an unsupported Ru−In bond with unsaturated Ru and In centres. 4 reacts with H2 to give [Ru(IPr)2(CO)(η2-H2)(InMe)(H)][BArF4], 5, while CO induces formation of the indyl complex [Ru(IPr)2(CO)3(InMe2)][BArF4], 7. These observations highlight the ability of Me to shuttle between Ru and In centres and are supported by DFT calculations on the mechanism of formation of 4 and its reactions with H2 and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe3 also involves CH4 loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η6 interaction of one aryl substituent with Ru.

AB - The hydride complex [Ru(IPr)2(CO)H][BArF4], 1, reacts with InMe3 with loss of CH4 to form [Ru(IPr)2(CO)(InMe)(Me)][BArF4], 4, featuring an unsupported Ru−In bond with unsaturated Ru and In centres. 4 reacts with H2 to give [Ru(IPr)2(CO)(η2-H2)(InMe)(H)][BArF4], 5, while CO induces formation of the indyl complex [Ru(IPr)2(CO)3(InMe2)][BArF4], 7. These observations highlight the ability of Me to shuttle between Ru and In centres and are supported by DFT calculations on the mechanism of formation of 4 and its reactions with H2 and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe3 also involves CH4 loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η6 interaction of one aryl substituent with Ru.

KW - density functional calculations

KW - gallium

KW - heterometallic complexes

KW - indium

KW - ruthenium

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JO - Chemistry - A European Journal

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ER -

Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium–Indium Bonds

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Keywords

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