Photochemistry of Cp′Mn(CO)2(NHC) (Cp′ = η5-C5H4Me) species: synthesis, time-resolved IR spectroscopy, and DFT calculations

Madeeha Batool, Thomas A. Martin, Andrés G. Algarra, Michael W. George, Stuart Alan Macgregor, Mary F. Mahon, Michael K. Whittlesey

Research output: Contribution to journalArticle

Abstract

UV irradiation of Cp'Mn(CO)(3) (Cp' = eta(5)-C5H4Me) in the presence of the free N-heterocyclic carbenes IEt2Me2, (IPr2Me2)-Pr-i, IMes, and IPr affords the NHC dicarbonyl complexes Cp'Mn(CO)(2)(NHC) (1-4). Time-resolved infrared spectroscopy in alkane solution reveals that 1-4 photodissociate CO to generate Cp'Mn(CO)(NHC) (1-CO, 2-CO, 3-CO, 4-CO), which exhibit solvent-independent second-order rate constants (k(CO)) for reaction with CO. These observations are consistent with 1-CO to 4-CO being stabilized by intramolecular agostic interactions with the NHCs rather than intermolecular alkane coordination. Density functional theory calculations provide support for this hypothesis and locate a series of agostic structures varying from delta-agostic (1-CO, 2-CO), to epsilon-agostic (3-CO), to phi-agostic (4-CO). The atoms-in-molecules approach is used to characterize these species, along with the gamma-agostic interaction seen in the CpMn(CO)(PPh3) analogue (5-CO), and shows that these species are distinguished primarily by the magnitude of the electron density at the agostic ring critical point.
Original languageEnglish
Pages (from-to)4971-4979
Number of pages9
JournalOrganometallics
Volume31
Issue number14
DOIs
Publication statusPublished - 23 Jul 2012

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Photochemical reactions
Carbon Monoxide
Discrete Fourier transforms
Infrared spectroscopy
Alkanes

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Batool, Madeeha ; Martin, Thomas A. ; Algarra, Andrés G. ; George, Michael W. ; Macgregor, Stuart Alan ; Mahon, Mary F. ; Whittlesey, Michael K. / Photochemistry of Cp′Mn(CO)2(NHC) (Cp′ = η5-C5H4Me) species: synthesis, time-resolved IR spectroscopy, and DFT calculations. In: Organometallics. 2012 ; Vol. 31, No. 14. pp. 4971-4979.
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abstract = "UV irradiation of Cp'Mn(CO)(3) (Cp' = eta(5)-C5H4Me) in the presence of the free N-heterocyclic carbenes IEt2Me2, (IPr2Me2)-Pr-i, IMes, and IPr affords the NHC dicarbonyl complexes Cp'Mn(CO)(2)(NHC) (1-4). Time-resolved infrared spectroscopy in alkane solution reveals that 1-4 photodissociate CO to generate Cp'Mn(CO)(NHC) (1-CO, 2-CO, 3-CO, 4-CO), which exhibit solvent-independent second-order rate constants (k(CO)) for reaction with CO. These observations are consistent with 1-CO to 4-CO being stabilized by intramolecular agostic interactions with the NHCs rather than intermolecular alkane coordination. Density functional theory calculations provide support for this hypothesis and locate a series of agostic structures varying from delta-agostic (1-CO, 2-CO), to epsilon-agostic (3-CO), to phi-agostic (4-CO). The atoms-in-molecules approach is used to characterize these species, along with the gamma-agostic interaction seen in the CpMn(CO)(PPh3) analogue (5-CO), and shows that these species are distinguished primarily by the magnitude of the electron density at the agostic ring critical point.",
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Photochemistry of Cp′Mn(CO)2(NHC) (Cp′ = η5-C5H4Me) species: synthesis, time-resolved IR spectroscopy, and DFT calculations. / Batool, Madeeha; Martin, Thomas A.; Algarra, Andrés G.; George, Michael W.; Macgregor, Stuart Alan; Mahon, Mary F.; Whittlesey, Michael K.

In: Organometallics, Vol. 31, No. 14, 23.07.2012, p. 4971-4979.

Research output: Contribution to journalArticle

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T1 - Photochemistry of Cp′Mn(CO)2(NHC) (Cp′ = η5-C5H4Me) species: synthesis, time-resolved IR spectroscopy, and DFT calculations

AU - Batool, Madeeha

AU - Martin, Thomas A.

AU - Algarra, Andrés G.

AU - George, Michael W.

AU - Macgregor, Stuart Alan

AU - Mahon, Mary F.

AU - Whittlesey, Michael K.

PY - 2012/7/23

Y1 - 2012/7/23

N2 - UV irradiation of Cp'Mn(CO)(3) (Cp' = eta(5)-C5H4Me) in the presence of the free N-heterocyclic carbenes IEt2Me2, (IPr2Me2)-Pr-i, IMes, and IPr affords the NHC dicarbonyl complexes Cp'Mn(CO)(2)(NHC) (1-4). Time-resolved infrared spectroscopy in alkane solution reveals that 1-4 photodissociate CO to generate Cp'Mn(CO)(NHC) (1-CO, 2-CO, 3-CO, 4-CO), which exhibit solvent-independent second-order rate constants (k(CO)) for reaction with CO. These observations are consistent with 1-CO to 4-CO being stabilized by intramolecular agostic interactions with the NHCs rather than intermolecular alkane coordination. Density functional theory calculations provide support for this hypothesis and locate a series of agostic structures varying from delta-agostic (1-CO, 2-CO), to epsilon-agostic (3-CO), to phi-agostic (4-CO). The atoms-in-molecules approach is used to characterize these species, along with the gamma-agostic interaction seen in the CpMn(CO)(PPh3) analogue (5-CO), and shows that these species are distinguished primarily by the magnitude of the electron density at the agostic ring critical point.

AB - UV irradiation of Cp'Mn(CO)(3) (Cp' = eta(5)-C5H4Me) in the presence of the free N-heterocyclic carbenes IEt2Me2, (IPr2Me2)-Pr-i, IMes, and IPr affords the NHC dicarbonyl complexes Cp'Mn(CO)(2)(NHC) (1-4). Time-resolved infrared spectroscopy in alkane solution reveals that 1-4 photodissociate CO to generate Cp'Mn(CO)(NHC) (1-CO, 2-CO, 3-CO, 4-CO), which exhibit solvent-independent second-order rate constants (k(CO)) for reaction with CO. These observations are consistent with 1-CO to 4-CO being stabilized by intramolecular agostic interactions with the NHCs rather than intermolecular alkane coordination. Density functional theory calculations provide support for this hypothesis and locate a series of agostic structures varying from delta-agostic (1-CO, 2-CO), to epsilon-agostic (3-CO), to phi-agostic (4-CO). The atoms-in-molecules approach is used to characterize these species, along with the gamma-agostic interaction seen in the CpMn(CO)(PPh3) analogue (5-CO), and shows that these species are distinguished primarily by the magnitude of the electron density at the agostic ring critical point.

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