Gas-Phase Chemistry of Methenyltricobalt Nonacarbonyl Radical Anions

David L. Vollmer; Michael L. Gross; Russell J. Waugh; Michael I. Bruce; John H. Bowie

doi:10.1021/om00021a032

Gas-Phase Chemistry of Methenyltricobalt Nonacarbonyl Radical Anions

David L. Vollmer, Michael L. Gross, Russell J. Waugh, Michael I. Bruce, John H. Bowie

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Abstract

The gas-phase chemistry of the radical anions of methenyltricobalt nonacarbonyls, YCCo₃-(CO)₉, where Y is H, CH₃, C₆H₅, C₆H₄F, CO₂CH₃, F, and Cl, is reported. Molecular anions are not stable, and YCCo₃(CO)_n fragments are formed by losses of carbon monoxide via dissociative electron capture. The fragmentation that occurs upon ionization (seen in full-scan mass spectra) or collisional activation (seen in tandem mass spectra) is minor and is in accord with the proposed electron-rich, delocalized core of the YCCo₃ moiety. Bimolecular reactions of the methenyltricobalt nonacarbonyl radical anions with their neutral precursor or with neutral ligands were studied by Fourier transform mass spectrometry (FTMS). The reactions with the neutral precursors result in higher-order clusters containing five or six cobalt atoms and both apical substituents (i.e., [(YC)₂Co₅(CO)₁₁]^- or [(YC)₂Co₆(CO)₁₃]^-). In mixtures of the methenyltricobalt nonacarbonyls with neutral ligands, substitution reactions are observed in which carbon monoxide is replaced by π-bonding ligands but not σ-bonding ligands.

Original language	English
Pages (from-to)	3564-3571
Number of pages	8
Journal	Organometallics
Volume	13
Issue number	9
DOIs	https://doi.org/10.1021/om00021a032
State	Published - Sep 1 1994

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@article{b7d5c22b8af549cba5a7f5a70539fc2b,

title = "Gas-Phase Chemistry of Methenyltricobalt Nonacarbonyl Radical Anions",

abstract = "The gas-phase chemistry of the radical anions of methenyltricobalt nonacarbonyls, YCCo3-(CO)9, where Y is H, CH3, C6H5, C6H4F, CO2CH3, F, and Cl, is reported. Molecular anions are not stable, and YCCo3(CO)n fragments are formed by losses of carbon monoxide via dissociative electron capture. The fragmentation that occurs upon ionization (seen in full-scan mass spectra) or collisional activation (seen in tandem mass spectra) is minor and is in accord with the proposed electron-rich, delocalized core of the YCCo3 moiety. Bimolecular reactions of the methenyltricobalt nonacarbonyl radical anions with their neutral precursor or with neutral ligands were studied by Fourier transform mass spectrometry (FTMS). The reactions with the neutral precursors result in higher-order clusters containing five or six cobalt atoms and both apical substituents (i.e., [(YC)2Co5(CO)11]- or [(YC)2Co6(CO)13]-). In mixtures of the methenyltricobalt nonacarbonyls with neutral ligands, substitution reactions are observed in which carbon monoxide is replaced by π-bonding ligands but not σ-bonding ligands.",

author = "Vollmer, {David L.} and Gross, {Michael L.} and Waugh, {Russell J.} and Bruce, {Michael I.} and Bowie, {John H.}",

year = "1994",

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doi = "10.1021/om00021a032",

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T1 - Gas-Phase Chemistry of Methenyltricobalt Nonacarbonyl Radical Anions

AU - Vollmer, David L.

AU - Gross, Michael L.

AU - Waugh, Russell J.

AU - Bruce, Michael I.

AU - Bowie, John H.

PY - 1994/9/1

Y1 - 1994/9/1

N2 - The gas-phase chemistry of the radical anions of methenyltricobalt nonacarbonyls, YCCo3-(CO)9, where Y is H, CH3, C6H5, C6H4F, CO2CH3, F, and Cl, is reported. Molecular anions are not stable, and YCCo3(CO)n fragments are formed by losses of carbon monoxide via dissociative electron capture. The fragmentation that occurs upon ionization (seen in full-scan mass spectra) or collisional activation (seen in tandem mass spectra) is minor and is in accord with the proposed electron-rich, delocalized core of the YCCo3 moiety. Bimolecular reactions of the methenyltricobalt nonacarbonyl radical anions with their neutral precursor or with neutral ligands were studied by Fourier transform mass spectrometry (FTMS). The reactions with the neutral precursors result in higher-order clusters containing five or six cobalt atoms and both apical substituents (i.e., [(YC)2Co5(CO)11]- or [(YC)2Co6(CO)13]-). In mixtures of the methenyltricobalt nonacarbonyls with neutral ligands, substitution reactions are observed in which carbon monoxide is replaced by π-bonding ligands but not σ-bonding ligands.

AB - The gas-phase chemistry of the radical anions of methenyltricobalt nonacarbonyls, YCCo3-(CO)9, where Y is H, CH3, C6H5, C6H4F, CO2CH3, F, and Cl, is reported. Molecular anions are not stable, and YCCo3(CO)n fragments are formed by losses of carbon monoxide via dissociative electron capture. The fragmentation that occurs upon ionization (seen in full-scan mass spectra) or collisional activation (seen in tandem mass spectra) is minor and is in accord with the proposed electron-rich, delocalized core of the YCCo3 moiety. Bimolecular reactions of the methenyltricobalt nonacarbonyl radical anions with their neutral precursor or with neutral ligands were studied by Fourier transform mass spectrometry (FTMS). The reactions with the neutral precursors result in higher-order clusters containing five or six cobalt atoms and both apical substituents (i.e., [(YC)2Co5(CO)11]- or [(YC)2Co6(CO)13]-). In mixtures of the methenyltricobalt nonacarbonyls with neutral ligands, substitution reactions are observed in which carbon monoxide is replaced by π-bonding ligands but not σ-bonding ligands.

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U2 - 10.1021/om00021a032

DO - 10.1021/om00021a032

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JO - Organometallics

JF - Organometallics

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ER -

Gas-Phase Chemistry of Methenyltricobalt Nonacarbonyl Radical Anions

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