Four-electron-donor hemilabile η3-PPh3 ligand that binds through a C=C bond rather than an agostic C-H interaction, and displacement of the C=C by methyl iodide or water

Tan Yun Cheng, David J. Szalda, Jonathan C. Hanson, James Muckerman, R Morris Bullock

Research output: Contribution to journalArticle

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Abstract

Hydride transfer from Cp(CO)2(PPh3)MoH to Ph 3C+BAr′4 - [Ar′ = 3,5-bis(trifluoromethyl)phenyl] produces [Cp(CO)23- PPh3)Mo]+[BArVP. Spectroscopic and crystallographic data indicate that one C=C of a Ph ring is weakly bound to the Mo, so that the PPh3 ligand is a four-electron-donor ligand. Computations (DFT/B3LYP and MP2 on [Cp(CO)23-PPh3)Mo]+ and [Cp(CO)2(η-PH2Ph)Mo]+, and DFT/B3LYP on [Cp(CO)23-PHtBuPh)Mo]+ and [Cp(CO)23-PH2Ph)Nb]) provide further information on the bonding and on the preference for bonding of the metal to the C=C bond rather than an agostic C-H interaction found in many related complexes. The hemilabile C=C bond is readily displaced by CH3I or H2O, and crystal structures are reported for [Cp(CO) 2(PPh3)Mo(ICH3)]+ and [Cp(CO) 2(PPh3)Mo(OH2)J+. The equilibrium constant for [Cp(CO)23-PPh3)Mo] + + ICH3 to give [Cp(CO)2(PPh 3)Mo(ICH3)]+ is Keq = 5.2 × 102 M-1 in CD2Cl2 at 22 °C.

Original languageEnglish
Pages (from-to)3785-3795
Number of pages11
JournalOrganometallics
Volume27
Issue number15
DOIs
Publication statusPublished - Aug 11 2008

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Carbon Monoxide
iodides
Ligands
ligands
Electrons
Water
water
hydrides
electrons
interactions
crystal structure
rings
metals
Discrete Fourier transforms
methyl iodide
Equilibrium constants
Hydrides
Crystal structure
Metals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Four-electron-donor hemilabile η3-PPh3 ligand that binds through a C=C bond rather than an agostic C-H interaction, and displacement of the C=C by methyl iodide or water. / Cheng, Tan Yun; Szalda, David J.; Hanson, Jonathan C.; Muckerman, James; Bullock, R Morris.

In: Organometallics, Vol. 27, No. 15, 11.08.2008, p. 3785-3795.

Research output: Contribution to journalArticle

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abstract = "Hydride transfer from Cp(CO)2(PPh3)MoH to Ph 3C+BAr′4 - [Ar′ = 3,5-bis(trifluoromethyl)phenyl] produces [Cp(CO)2(η3- PPh3)Mo]+[BArVP. Spectroscopic and crystallographic data indicate that one C=C of a Ph ring is weakly bound to the Mo, so that the PPh3 ligand is a four-electron-donor ligand. Computations (DFT/B3LYP and MP2 on [Cp(CO)2(η3-PPh3)Mo]+ and [Cp(CO)2(η-PH2Ph)Mo]+, and DFT/B3LYP on [Cp(CO)2(η3-PHtBuPh)Mo]+ and [Cp(CO)2(η3-PH2Ph)Nb]) provide further information on the bonding and on the preference for bonding of the metal to the C=C bond rather than an agostic C-H interaction found in many related complexes. The hemilabile C=C bond is readily displaced by CH3I or H2O, and crystal structures are reported for [Cp(CO) 2(PPh3)Mo(ICH3)]+ and [Cp(CO) 2(PPh3)Mo(OH2)J+. The equilibrium constant for [Cp(CO)2(η3-PPh3)Mo] + + ICH3 to give [Cp(CO)2(PPh 3)Mo(ICH3)]+ is Keq = 5.2 × 102 M-1 in CD2Cl2 at 22 °C.",
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T1 - Four-electron-donor hemilabile η3-PPh3 ligand that binds through a C=C bond rather than an agostic C-H interaction, and displacement of the C=C by methyl iodide or water

AU - Cheng, Tan Yun

AU - Szalda, David J.

AU - Hanson, Jonathan C.

AU - Muckerman, James

AU - Bullock, R Morris

PY - 2008/8/11

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N2 - Hydride transfer from Cp(CO)2(PPh3)MoH to Ph 3C+BAr′4 - [Ar′ = 3,5-bis(trifluoromethyl)phenyl] produces [Cp(CO)2(η3- PPh3)Mo]+[BArVP. Spectroscopic and crystallographic data indicate that one C=C of a Ph ring is weakly bound to the Mo, so that the PPh3 ligand is a four-electron-donor ligand. Computations (DFT/B3LYP and MP2 on [Cp(CO)2(η3-PPh3)Mo]+ and [Cp(CO)2(η-PH2Ph)Mo]+, and DFT/B3LYP on [Cp(CO)2(η3-PHtBuPh)Mo]+ and [Cp(CO)2(η3-PH2Ph)Nb]) provide further information on the bonding and on the preference for bonding of the metal to the C=C bond rather than an agostic C-H interaction found in many related complexes. The hemilabile C=C bond is readily displaced by CH3I or H2O, and crystal structures are reported for [Cp(CO) 2(PPh3)Mo(ICH3)]+ and [Cp(CO) 2(PPh3)Mo(OH2)J+. The equilibrium constant for [Cp(CO)2(η3-PPh3)Mo] + + ICH3 to give [Cp(CO)2(PPh 3)Mo(ICH3)]+ is Keq = 5.2 × 102 M-1 in CD2Cl2 at 22 °C.

AB - Hydride transfer from Cp(CO)2(PPh3)MoH to Ph 3C+BAr′4 - [Ar′ = 3,5-bis(trifluoromethyl)phenyl] produces [Cp(CO)2(η3- PPh3)Mo]+[BArVP. Spectroscopic and crystallographic data indicate that one C=C of a Ph ring is weakly bound to the Mo, so that the PPh3 ligand is a four-electron-donor ligand. Computations (DFT/B3LYP and MP2 on [Cp(CO)2(η3-PPh3)Mo]+ and [Cp(CO)2(η-PH2Ph)Mo]+, and DFT/B3LYP on [Cp(CO)2(η3-PHtBuPh)Mo]+ and [Cp(CO)2(η3-PH2Ph)Nb]) provide further information on the bonding and on the preference for bonding of the metal to the C=C bond rather than an agostic C-H interaction found in many related complexes. The hemilabile C=C bond is readily displaced by CH3I or H2O, and crystal structures are reported for [Cp(CO) 2(PPh3)Mo(ICH3)]+ and [Cp(CO) 2(PPh3)Mo(OH2)J+. The equilibrium constant for [Cp(CO)2(η3-PPh3)Mo] + + ICH3 to give [Cp(CO)2(PPh 3)Mo(ICH3)]+ is Keq = 5.2 × 102 M-1 in CD2Cl2 at 22 °C.

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