Metal Complexes of Unsaturated Tertiary Phosphines and Arsines. III. Group VI Metal-Olefin Complexes. An Unusual Metal-Catalyzed Olefin Isomerization

来自 ACS

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摘要：

The preparation of a new chelating ligand, 2-allylphenyldiphenylphosphine (AP), and its application to the synthesis of the first monoolefin complexes of all three zerovalent group VI metals are described. The molecular formula of these complexes [C21H19PM(CO)4; M = Cr, Mo, W] and their infrared spectra are consistent with coordination of both the phosphorus atom and a C=C bond to the group VI metal. However, nmr results show that the position of the C=C bond has been shifted upon coordination of the olefin to the metal and that the ligand in these complexes is the isomeric compound, 2-propenylphenyldiphenylphosphine. Moreover, by independent synthesis of both the cis and trans forms of this propenyl ligand and their corresponding group VI metal complexes it has been possible to show further that the coordinated olefin has the cis configuration. This isomerization of AP to the higher energy isomer of 2-propenylphenyldiphenylphosphine is discussed in light of previous transition metal catalyzed olefin isomerizations. The lowering in the C=C stretching frequency upon coordination of 2-cis-propenylphenyldiphenylphosphine to the zerovalent group VI metals is determined from infrared spectral measurements and is used to assess the degree of interaction between olefin and metal in these complexes.

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DOI：

10.1021/ic50046a029

被引量：

101

年份：

1966