Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium-Indium Bonds

Ian Riddlestone; Nasir Rajabi; Stuart Macgregor; Mary Mahon; Michael Whittlesey

doi:10.1002/chem.201705796

Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium-Indium Bonds

Ian Riddlestone, Nasir Rajabi, Stuart Macgregor, Mary Mahon, Michael Whittlesey

Department of Chemistry

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

13 Citations (SciVal)

44 Downloads (Pure)

Abstract

The hydride complex [Ru(IPr) ₂(CO)H][BAr ^F ₄], 1, reacts with InMe ₃ with loss of CH ₄ to form [Ru(IPr) ₂(CO)(InMe)(Me)][BAr ^F ₄], 4, featuring an unsupported Ru−In bond with unsaturated Ru and In centres. 4 reacts with H ₂ to give [Ru(IPr) ₂(CO)(η ²-H ₂)(InMe)(H)][BAr ^F ₄], 5, while CO induces formation of the indyl complex [Ru(IPr) ₂(CO) ₃(InMe ₂)][BAr ^F ₄], 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 H ₂ and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe ₃ also involves CH ₄ loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η ⁶ 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
Early online date	4 Jan 2018
DOIs	https://doi.org/10.1002/chem.201705796
Publication status	Published - 1 Feb 2018

Keywords

density functional calculations
gallium
heterometallic complexes
indium
ruthenium

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.201705796

chem.201705796 for PURE
This is the peer reviewed version of the following article: I. M. Riddlestone, N. A. Rajabi, S. A. Macgregor, M. F. Mahon, M. K. Whittlesey, Well‐Defined Heterobimetallic Reactivity at Unsupported Ruthenium–Indium Bonds, Chem. Eur. J. 2018, 24, 1732, which has been published in final form athttps://doi.org/10.1002/chem.201705796. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
Accepted author manuscript, 1.14 MB

Cite this

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

abstract = "The hydride complex [Ru(IPr) 2(CO)H][BAr F 4], 1, reacts with InMe 3 with loss of CH 4 to form [Ru(IPr) 2(CO)(InMe)(Me)][BAr F 4], 4, featuring an unsupported Ru−In bond with unsaturated Ru and In centres. 4 reacts with H 2 to give [Ru(IPr) 2(CO)(η 2-H 2)(InMe)(H)][BAr F 4], 5, while CO induces formation of the indyl complex [Ru(IPr) 2(CO) 3(InMe 2)][BAr F 4], 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 H 2 and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe 3 also involves CH 4 loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η 6 interaction of one aryl substituent with Ru. ",

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

author = "Ian Riddlestone and Nasir Rajabi and Stuart Macgregor and Mary Mahon and Michael Whittlesey",

year = "2018",

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day = "1",

doi = "10.1002/chem.201705796",

language = "English",

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T1 - Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium-Indium Bonds

AU - Riddlestone, Ian

AU - Rajabi, Nasir

AU - Macgregor, Stuart

AU - Mahon, Mary

AU - Whittlesey, Michael

PY - 2018/2/1

Y1 - 2018/2/1

N2 - The hydride complex [Ru(IPr) 2(CO)H][BAr F 4], 1, reacts with InMe 3 with loss of CH 4 to form [Ru(IPr) 2(CO)(InMe)(Me)][BAr F 4], 4, featuring an unsupported Ru−In bond with unsaturated Ru and In centres. 4 reacts with H 2 to give [Ru(IPr) 2(CO)(η 2-H 2)(InMe)(H)][BAr F 4], 5, while CO induces formation of the indyl complex [Ru(IPr) 2(CO) 3(InMe 2)][BAr F 4], 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 H 2 and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe 3 also involves CH 4 loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η 6 interaction of one aryl substituent with Ru.

AB - The hydride complex [Ru(IPr) 2(CO)H][BAr F 4], 1, reacts with InMe 3 with loss of CH 4 to form [Ru(IPr) 2(CO)(InMe)(Me)][BAr F 4], 4, featuring an unsupported Ru−In bond with unsaturated Ru and In centres. 4 reacts with H 2 to give [Ru(IPr) 2(CO)(η 2-H 2)(InMe)(H)][BAr F 4], 5, while CO induces formation of the indyl complex [Ru(IPr) 2(CO) 3(InMe 2)][BAr F 4], 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 H 2 and CO. An analysis of Ru-In bonding in these species is also presented. Reaction of 1 with GaMe 3 also involves CH 4 loss but, in contrast to its In congener, sees IPr transfer from Ru to Ga to give a gallyl complex featuring an η 6 interaction of one aryl substituent with Ru.

KW - density functional calculations

KW - gallium

KW - heterometallic complexes

KW - indium

KW - ruthenium

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U2 - 10.1002/chem.201705796

DO - 10.1002/chem.201705796

M3 - Article

SN - 0947-6539

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SP - 1732

EP - 1738

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 7

ER -

Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium-Indium Bonds

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Catalytic Functionalisation of Aromatic Fluorocarbons

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Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium-Indium Bonds

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ASJC Scopus subject areas

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Catalytic Functionalisation of Aromatic Fluorocarbons

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