Searching for the hidden hydrides: the competition between alkene isomerization and metathesis with Grubbs catalysts

Ian W. Ashworth; Ian H. Hillier; David J Nelson; Jonathan M Percy; Mark A. Vincent

doi:10.1002/ejoc.201201036

Searching for the hidden hydrides: the competition between alkene isomerization and metathesis with Grubbs catalysts

Ian W. Ashworth, Ian H. Hillier, David J Nelson, Jonathan M Percy, Mark A. Vincent

Pure And Applied Chemistry

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

34 Citations (Scopus)

Abstract

Although Grubbs metathesis catalysts have enabled syntheses of a range of molecules, alkene isomerization, a known and problematic side reaction, is poorly understood. Several mechanisms which have been advanced to account for isomerization were studied by using electronic structure calculations. The pathway catalyzed by a ruthenium hydride emerged as the most facile process by a significant margin. For the first time, we have obtained experimental evidence for the presence of this species in a metathesis-active system.

Original language	English
Pages (from-to)	5673–5677
Number of pages	5
Journal	European Journal of Organic Chemistry
Volume	2012
Issue number	29
DOIs	https://doi.org/10.1002/ejoc.201201036
Publication status	Published - Oct 2012

Keywords

ruthenium
metathesis
homogeneous catalysis
density functional calculations
kinetics

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10.1002/ejoc.201201036

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2 Finished

Quantifying the Interplay of Structure and Reactivity in Ring Closing Metathesis (QuIStRiC)
Percy, J.
EPSRC (Engineering and Physical Sciences Research Council)
1/04/09 → 31/07/12
Project: Research
Physical Organic Chemistry: Opportunities In Synthesis, Materials And Pharmaceuticals (Science And Innovation Award)
Murphy, J., Coombs, G., Ferguson, A. & Florence, A.
Scottish Funding Council SFC, EPSRC (Engineering and Physical Sciences Research Council)
1/09/07 → 30/10/12
Project: Research

Cite this

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title = "Searching for the hidden hydrides: the competition between alkene isomerization and metathesis with Grubbs catalysts",

abstract = "Although Grubbs metathesis catalysts have enabled syntheses of a range of molecules, alkene isomerization, a known and problematic side reaction, is poorly understood. Several mechanisms which have been advanced to account for isomerization were studied by using electronic structure calculations. The pathway catalyzed by a ruthenium hydride emerged as the most facile process by a significant margin. For the first time, we have obtained experimental evidence for the presence of this species in a metathesis-active system.",

keywords = "ruthenium, metathesis, homogeneous catalysis, density functional calculations, kinetics",

author = "Ashworth, {Ian W.} and Hillier, {Ian H.} and Nelson, {David J} and Percy, {Jonathan M} and Vincent, {Mark A.}",

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AU - Ashworth, Ian W.

AU - Hillier, Ian H.

AU - Nelson, David J

AU - Percy, Jonathan M

AU - Vincent, Mark A.

PY - 2012/10

Y1 - 2012/10

N2 - Although Grubbs metathesis catalysts have enabled syntheses of a range of molecules, alkene isomerization, a known and problematic side reaction, is poorly understood. Several mechanisms which have been advanced to account for isomerization were studied by using electronic structure calculations. The pathway catalyzed by a ruthenium hydride emerged as the most facile process by a significant margin. For the first time, we have obtained experimental evidence for the presence of this species in a metathesis-active system.

AB - Although Grubbs metathesis catalysts have enabled syntheses of a range of molecules, alkene isomerization, a known and problematic side reaction, is poorly understood. Several mechanisms which have been advanced to account for isomerization were studied by using electronic structure calculations. The pathway catalyzed by a ruthenium hydride emerged as the most facile process by a significant margin. For the first time, we have obtained experimental evidence for the presence of this species in a metathesis-active system.

KW - ruthenium

KW - metathesis

KW - homogeneous catalysis

KW - density functional calculations

KW - kinetics

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U2 - 10.1002/ejoc.201201036

DO - 10.1002/ejoc.201201036

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JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 29

ER -

Searching for the hidden hydrides: the competition between alkene isomerization and metathesis with Grubbs catalysts

Abstract

Keywords

Access to Document

Quantifying the Interplay of Structure and Reactivity in Ring Closing Metathesis (QuIStRiC)

Physical Organic Chemistry: Opportunities In Synthesis, Materials And Pharmaceuticals (Science And Innovation Award)

Cite this