Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: In situ photolysis, parahydrogen, and computational studies

Kirsten A M Ampt; Suzanne Burling; Steven M A Donald; Susie Douglas; Simon B Duckett; Stuart A Macgregor; Robin N Perutz; Michael K Whittlesey

doi:10.1021/ja0622397

Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: In situ photolysis, parahydrogen, and computational studies

Kirsten A M Ampt, Suzanne Burling, Steven M A Donald, Susie Douglas, Simon B Duckett, Stuart A Macgregor, Robin N Perutz, Michael K Whittlesey

Department of Chemistry

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

25 Citations (SciVal)

Abstract

Low-temp. UV irradn. of the N-heterocyclic carbene complex Ru(IEt2Me2)(PPh3)2(CO)H2 (IEt2Me2 = 1,3-diethyl-1,3-dihydro-4,5-dimethyl-2H-imidazol-2-ylidene) leads to a remarkable photoisomerization reaction. By combining in situ photolysis and parahydrogen expts. to characterize the ultimate photoproducts and DFT calcns. to interrogate the structures of the key 16-electron intermediates, the importance of both PPh3 and H2 loss pathways was established.

Original language	English
Pages (from-to)	7452-7453
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	128
Issue number	23
DOIs	https://doi.org/10.1021/ja0622397
Publication status	Published - 2006

Keywords

Zero point energy (in situ photolysis
Potential energy surface
in situ photolysis
nonpreparative)
heterocyclic carbene ruthenium carbonyl hydrido phosphine photoisomerization kinetics mechanism
of ruthenium heterocyclic-carbene carbonyl hydrido phosphine isomeric complexes and photoisomerization intermediates)
parahydrogen
PROC (Pr
engineering or chemical process)
Total energy
Density functional theory
unclassified)
FMU (Formation
Isomerization
PRP (Properties)
FORM (Formation
and computational studies of photochem. isomerization of N-heterocyclic-carbene ruthenium carbonyl hydride phosphine complex)
RCT (Reactant)
PREP (Preparation)
Isomerization kinetics (photoisomerization
ruthenium imidazolinylidene carbonyl hydrido phosphine photoisomerization mechanism expt theory
PEP (Physical
CPS (Chemical process)
Carbene complexes Role
Molecular structure (optimized
SPN (Synthetic preparation)

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10.1021/ja0622397

Cite this

Ampt, K. A. M., Burling, S., Donald, S. M. A., Douglas, S., Duckett, S. B., Macgregor, S. A., Perutz, R. N., & Whittlesey, M. K. (2006). Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: In situ photolysis, parahydrogen, and computational studies. Journal of the American Chemical Society, 128(23), 7452-7453. https://doi.org/10.1021/ja0622397

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title = "Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: In situ photolysis, parahydrogen, and computational studies",

abstract = "Low-temp. UV irradn. of the N-heterocyclic carbene complex Ru(IEt2Me2)(PPh3)2(CO)H2 (IEt2Me2 = 1,3-diethyl-1,3-dihydro-4,5-dimethyl-2H-imidazol-2-ylidene) leads to a remarkable photoisomerization reaction. By combining in situ photolysis and parahydrogen expts. to characterize the ultimate photoproducts and DFT calcns. to interrogate the structures of the key 16-electron intermediates, the importance of both PPh3 and H2 loss pathways was established.",

keywords = "Zero point energy (in situ photolysis, Potential energy surface, in situ photolysis, nonpreparative), heterocyclic carbene ruthenium carbonyl hydrido phosphine photoisomerization kinetics mechanism, of ruthenium heterocyclic-carbene carbonyl hydrido phosphine isomeric complexes and photoisomerization intermediates), parahydrogen, PROC (Pr, engineering or chemical process), Total energy, Density functional theory, unclassified), FMU (Formation, Isomerization, PRP (Properties), FORM (Formation, and computational studies of photochem. isomerization of N-heterocyclic-carbene ruthenium carbonyl hydride phosphine complex), RCT (Reactant), PREP (Preparation), Isomerization kinetics (photoisomerization, ruthenium imidazolinylidene carbonyl hydrido phosphine photoisomerization mechanism expt theory, PEP (Physical, CPS (Chemical process), Carbene complexes Role, Molecular structure (optimized, SPN (Synthetic preparation)",

author = "Ampt, {Kirsten A M} and Suzanne Burling and Donald, {Steven M A} and Susie Douglas and Duckett, {Simon B} and Macgregor, {Stuart A} and Perutz, {Robin N} and Whittlesey, {Michael K}",

year = "2006",

doi = "10.1021/ja0622397",

language = "English",

volume = "128",

pages = "7452--7453",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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AU - Ampt, Kirsten A M

AU - Burling, Suzanne

AU - Donald, Steven M A

AU - Douglas, Susie

AU - Duckett, Simon B

AU - Macgregor, Stuart A

AU - Perutz, Robin N

AU - Whittlesey, Michael K

PY - 2006

Y1 - 2006

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AB - Low-temp. UV irradn. of the N-heterocyclic carbene complex Ru(IEt2Me2)(PPh3)2(CO)H2 (IEt2Me2 = 1,3-diethyl-1,3-dihydro-4,5-dimethyl-2H-imidazol-2-ylidene) leads to a remarkable photoisomerization reaction. By combining in situ photolysis and parahydrogen expts. to characterize the ultimate photoproducts and DFT calcns. to interrogate the structures of the key 16-electron intermediates, the importance of both PPh3 and H2 loss pathways was established.

KW - Zero point energy (in situ photolysis

KW - Potential energy surface

KW - in situ photolysis

KW - nonpreparative)

KW - heterocyclic carbene ruthenium carbonyl hydrido phosphine photoisomerization kinetics mechanism

KW - of ruthenium heterocyclic-carbene carbonyl hydrido phosphine isomeric complexes and photoisomerization intermediates)

KW - parahydrogen

KW - PROC (Pr

KW - engineering or chemical process)

KW - Total energy

KW - Density functional theory

KW - unclassified)

KW - FMU (Formation

KW - Isomerization

KW - PRP (Properties)

KW - FORM (Formation

KW - and computational studies of photochem. isomerization of N-heterocyclic-carbene ruthenium carbonyl hydride phosphine complex)

KW - RCT (Reactant)

KW - PREP (Preparation)

KW - Isomerization kinetics (photoisomerization

KW - ruthenium imidazolinylidene carbonyl hydrido phosphine photoisomerization mechanism expt theory

KW - PEP (Physical

KW - CPS (Chemical process)

KW - Carbene complexes Role

KW - Molecular structure (optimized

KW - SPN (Synthetic preparation)

UR - http://dx.doi.org/10.1021/ja0622397

U2 - 10.1021/ja0622397

DO - 10.1021/ja0622397

M3 - Article

SN - 0002-7863

VL - 128

SP - 7452

EP - 7453

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: In situ photolysis, parahydrogen, and computational studies

Abstract

Keywords

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500 MHZ NMR SPECTROMETER TO SUPPORT ORGANIC, BIO-ORGANIC AND INORGANIC CHEMISTRY

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Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: In situ photolysis, parahydrogen, and computational studies

Abstract

Keywords

Access to Document

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500 MHZ NMR SPECTROMETER TO SUPPORT ORGANIC, BIO-ORGANIC AND INORGANIC CHEMISTRY

Cite this