摘要：

This paper reports a variety of metal carbonyl complexes of the highly basic small-bite bidentate bis(tertiary phosphine) (CH3)2PCH2P(CH3)2 (abbreviated as dmpm). Thus, displacement of the coordinated norbornadiene in C7H8M(CO)4 (M = Cr, Mo, W) with dmpm gives the corresponding pale yellow mononuclear chelates (dmpm)M(CO)4. Similarly, displacement of the coordinated cycloheptatriene in C7H8M(CO)3 (M = Cr, Mo, W) with dmpm gives the corresponding yellow binuclear complexes fac-(dmpm)3M2(CO)6 shown by their NMR spectra to contain one bridging and two chelating dmpm ligands. The chromium complex fac-(dmpm)3Cr2(CO)6 is unstable in solution, being converted ultimately to yellow mer-(dmpm)2Cr(CO)3 in which one of the dmpm ligands is monodentate with an uncomplexed P(CH3)2 unit. The phosphorus-31 NMR spectrum of mer-(dmpm)2Cr(CO)3 is compared with that of fac-(dmpm)2W(CO)3, one of the products obtained by the photolysis of W(CO)6 with dmpm. The acetonitrile complexes fac-(CH3CN)3M(CO)3 (M = Mo, W) react with dmpm in boiling acetonitrile to give fac-(dmpm)3M(CO)3 containing three monodentate dmpm ligands. Thermal reactions of M2(CO)10 (M = Mn, Re) with dmpm under various conditions give binuclear complexes of the type (dmpm)nM2(CO)10-2n (M = Mn, n = 1 and 2; M = Re, n = 2) containing five-membered bimetallic chelate rings. The orange to red binuclear iron carbonyl complexes (dmpm)nFe2(CO)9-2n are obtained from the reaction of dmpm with Fe2(CO)9 at room temperature (n = 1) and by the photolysis of dmpm with Fe(CO)5 (n = 2). Reactions of dmpm with the cyclopentadienyl metal carbonyls C5H5Mn(CO)3 and [C5H5Fe(CO)2]2 give yellow pyrophoric (dmpm)Mn(CO)(C5H5) and green (dmpm)Fe2(CO)2(C5H5)2, respectively. The nickel carbonyls Ni(CO)4 and [C5H5NiCO]2 react with dmpm to give white air-sensitive (dmpm)Ni(CO)2 and yellow relatively air-stable (dmpm)3Ni2(CO)2.

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