Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction

R. F. R. Jazzar; Maurizio Varrone; Andrew D. Burrows; Stuart A. Macgregor; Mary F. Mahon; Michael K. Whittlesey

doi:10.1016/j.ica.2005.05.021

Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction

R. F. R. Jazzar, Maurizio Varrone, Andrew D. Burrows, Stuart A. Macgregor, Mary F. Mahon, Michael K. Whittlesey

School of Engineering & Physical Sciences

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

17 Citations (Scopus)

Abstract

Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh ₃)₂(CO)(NC₄H₃C(O)CH₃)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (?H^‡ = 195 ± 41 kJ mol^-1; ?S^‡ = 232 ± 62 J mol ^-1 K^-1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2'-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.

Original language	English
Pages (from-to)	815-820
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	359
Issue number	3
DOIs	https://doi.org/10.1016/j.ica.2005.05.021
Publication status	Published - 1 Feb 2006

Keywords

Cyclometallation
Density functional theory
Hydride ligands
Murai reaction
Phosphine ligands
Ruthenium complexes

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10.1016/j.ica.2005.05.021

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title = "Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction",

abstract = "Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh 3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (?H‡ = 195 ± 41 kJ mol-1; ?S‡ = 232 ± 62 J mol -1 K-1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2'-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.",

keywords = "Cyclometallation, Density functional theory, Hydride ligands, Murai reaction, Phosphine ligands, Ruthenium complexes",

author = "Jazzar, {R. F. R.} and Maurizio Varrone and Burrows, {Andrew D.} and Macgregor, {Stuart A.} and Mahon, {Mary F.} and Whittlesey, {Michael K.}",

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doi = "10.1016/j.ica.2005.05.021",

language = "English",

volume = "359",

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journal = "Inorganica Chimica Acta",

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T1 - Synthesis and isomerisation of two metallated N,O-complexes of ruthenium

T2 - Models for the Murai reaction

AU - Jazzar, R. F. R.

AU - Varrone, Maurizio

AU - Burrows, Andrew D.

AU - Macgregor, Stuart A.

AU - Mahon, Mary F.

AU - Whittlesey, Michael K.

PY - 2006/2/1

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N2 - Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh 3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (?H‡ = 195 ± 41 kJ mol-1; ?S‡ = 232 ± 62 J mol -1 K-1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2'-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.

AB - Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh 3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (?H‡ = 195 ± 41 kJ mol-1; ?S‡ = 232 ± 62 J mol -1 K-1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2'-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.

KW - Cyclometallation

KW - Density functional theory

KW - Hydride ligands

KW - Murai reaction

KW - Phosphine ligands

KW - Ruthenium complexes

U2 - 10.1016/j.ica.2005.05.021

DO - 10.1016/j.ica.2005.05.021

M3 - Article

SN - 0020-1693

VL - 359

SP - 815

EP - 820

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 3

ER -

Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction

Abstract

Keywords

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