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

Rodolphe 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

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

Department of Chemistry

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

17 Citations (SciVal)

Abstract

Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh3)(2)(Co)(NC4H3C(O)CH3)H] {cis-NH (1) and trans-NH (2) have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to I upon heating via a dissociative pathway (Delta H++ = 195 +/- 41 kJ mol(-1); Delta 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 - Feb 2006

Keywords

Molecular structure (of isomeric ruthenium(II) N
O-coordinated acetylpyrrolyl hydrido carbonyl bis(phosphine) complex related to Murai coupling catalysts)
O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes as models for catalytic intermediates in Murai coupling reaction)
O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes)
crystal structure ruthenium acetylpyrrolyl hydride carbonyl phosphine isomer
O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complex isomers as models for catalytic intermediates in Murai coupling reaction)
Transition state structure (in isomerization of ruthenium(II) N
ruthenium acetylpyrrolyl hydride carbonyl phosphine complex prepn structure isomerization
Isomerization (of ruthenium(II) N
isomerization ruthenium acetylpyrrolyl hydride carbonyl phosphine complex thermodn
Isomerization enthalpy (of isomeric ruthenium(II) N
Activation entropy (for isomerization of isomeric ruthenium(II) N
Crystal structure
Murai coupling catalyst intermediate ruthenium acetylpyrrolyl hydride carbonyl phosphine
Coupling reaction catalysts (Murai
prepn. of ruthenium(II) N

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10.1016/j.ica.2005.05.021

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@article{888fad28d130403ca92620f551b06d76,

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(PPh3)(2)(Co)(NC4H3C(O)CH3)H] {cis-NH (1) and trans-NH (2) have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to I upon heating via a dissociative pathway (Delta H++ = 195 +/- 41 kJ mol(-1); Delta 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 = "Molecular structure (of isomeric ruthenium(II) N, O-coordinated acetylpyrrolyl hydrido carbonyl bis(phosphine) complex related to Murai coupling catalysts), O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes as models for catalytic intermediates in Murai coupling reaction), O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes), crystal structure ruthenium acetylpyrrolyl hydride carbonyl phosphine isomer, O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complex isomers as models for catalytic intermediates in Murai coupling reaction), Transition state structure (in isomerization of ruthenium(II) N, ruthenium acetylpyrrolyl hydride carbonyl phosphine complex prepn structure isomerization, Isomerization (of ruthenium(II) N, isomerization ruthenium acetylpyrrolyl hydride carbonyl phosphine complex thermodn, Isomerization enthalpy (of isomeric ruthenium(II) N, Activation entropy (for isomerization of isomeric ruthenium(II) N, Crystal structure, Murai coupling catalyst intermediate ruthenium acetylpyrrolyl hydride carbonyl phosphine, Coupling reaction catalysts (Murai, prepn. of ruthenium(II) N",

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

year = "2006",

month = feb,

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

language = "English",

volume = "359",

pages = "815--820",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier B.V.",

number = "3",

}

TY - JOUR

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

T2 - models for the Murai reaction

AU - Jazzar, Rodolphe F. R.

AU - Varrone, Maurizio

AU - Burrows, Andrew D.

AU - Macgregor, Stuart A.

AU - Mahon, Mary F.

AU - Whittlesey, Michael K.

PY - 2006/2

Y1 - 2006/2

N2 - Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh3)(2)(Co)(NC4H3C(O)CH3)H] {cis-NH (1) and trans-NH (2) have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to I upon heating via a dissociative pathway (Delta H++ = 195 +/- 41 kJ mol(-1); Delta 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(PPh3)(2)(Co)(NC4H3C(O)CH3)H] {cis-NH (1) and trans-NH (2) have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to I upon heating via a dissociative pathway (Delta H++ = 195 +/- 41 kJ mol(-1); Delta 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 - Molecular structure (of isomeric ruthenium(II) N

KW - O-coordinated acetylpyrrolyl hydrido carbonyl bis(phosphine) complex related to Murai coupling catalysts)

KW - O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes as models for catalytic intermediates in Murai coupling reaction)

KW - O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes)

KW - crystal structure ruthenium acetylpyrrolyl hydride carbonyl phosphine isomer

KW - O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complex isomers as models for catalytic intermediates in Murai coupling reaction)

KW - Transition state structure (in isomerization of ruthenium(II) N

KW - ruthenium acetylpyrrolyl hydride carbonyl phosphine complex prepn structure isomerization

KW - Isomerization (of ruthenium(II) N

KW - isomerization ruthenium acetylpyrrolyl hydride carbonyl phosphine complex thermodn

KW - Isomerization enthalpy (of isomeric ruthenium(II) N

KW - Activation entropy (for isomerization of isomeric ruthenium(II) N

KW - Crystal structure

KW - Murai coupling catalyst intermediate ruthenium acetylpyrrolyl hydride carbonyl phosphine

KW - Coupling reaction catalysts (Murai

KW - prepn. of ruthenium(II) N

UR - http://dx.doi.org/10.1016/j.ica.2005.05.021

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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