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

Heriot-Watt University

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

16 Citations (SciVal)

80 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

Access to Document

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",

month = feb,

day = "1",

doi = "10.1002/chem.201705796",

language = "English",

volume = "24",

pages = "1732--1738",

journal = "Chemistry - A European Journal",

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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

VL - 24

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

Abstract

Keywords

ASJC Scopus subject areas

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Catalytic Functionalisation of Aromatic Fluorocarbons

Avance III 500 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (9West)

Avance NEO 500 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)

Raman confocal microscope RENISHAM INVIA

Cite this

Well-Defined Heterobimetallic Reactivity at Unsupported Ruthenium-Indium Bonds

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

Catalytic Functionalisation of Aromatic Fluorocarbons

Equipment

Avance III 500 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (9West)

Avance NEO 500 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)

Raman confocal microscope RENISHAM INVIA

Cite this