Dihapto-Coordinated Amide, Ester, and Aldehyde Complexes and Their Role in Decarbonylation

Dihapto-Coordinated Amide, Ester, and Aldehyde Complexes and Their Role in Decarbonylation

The π-basic metal fragment {TpW(NO)(PMe3)} forms thermally stable η2 complexes with acetaldehyde, acetone, ethyl acetate, methyl formate, and N,N-dimethylformamide (where Tp = hydridotris(pyrazolyl)borate). The related system {TpMo(NO)(MeIm)} (MeIm = 1-methylimidazole) also forms stable η2 complexes...

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Veröffentlicht in:Organometallics 2005-02, Vol.24 (5), p.911-919
Hauptverfasser: Graham, Peter M, Mocella, Christopher J, Sabat, Michal, Harman, W. Dean
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Mocella, Christopher J
Sabat, Michal
Harman, W. Dean
description The π-basic metal fragment {TpW(NO)(PMe3)} forms thermally stable η2 complexes with acetaldehyde, acetone, ethyl acetate, methyl formate, and N,N-dimethylformamide (where Tp = hydridotris(pyrazolyl)borate). The related system {TpMo(NO)(MeIm)} (MeIm = 1-methylimidazole) also forms stable η2 complexes with acetone, methyl formate, and N,N-dimethylformamide. When the tungsten fragment is combined with a carboxylic acid, oxidative addition yields a seven-coordinate hydride complex. These results are compared to those observed for analogous Re and Os systems. TpMo(NO)(MeIm)(η 2 -DMF) and TpW(NO)(PMe3)(η 2 -DMF) are rare examples of η2 amide complexes, demonstrating the exceptional strength of these group 6 π bases.
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Dean</creator><creatorcontrib>Graham, Peter M ; Mocella, Christopher J ; Sabat, Michal ; Harman, W. Dean</creatorcontrib><description>The π-basic metal fragment {TpW(NO)(PMe3)} forms thermally stable η2 complexes with acetaldehyde, acetone, ethyl acetate, methyl formate, and N,N-dimethylformamide (where Tp = hydridotris(pyrazolyl)borate). The related system {TpMo(NO)(MeIm)} (MeIm = 1-methylimidazole) also forms stable η2 complexes with acetone, methyl formate, and N,N-dimethylformamide. When the tungsten fragment is combined with a carboxylic acid, oxidative addition yields a seven-coordinate hydride complex. These results are compared to those observed for analogous Re and Os systems. 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