Bimetallic Complexes from Amphoteric Group 13/15 Ligands: Syntheses and X-ray Crystal Structrures

摘要

Bimetallic, pentel-bridged complexes of the type [(dmap)Me_2-M-C(SiMe_3)_2-M'(CO)_n] (M=Al, Ga; E=P, As, Sb; M'=Cr, Fe, Ni; DMAP=4-(dimethylamino)pyridine) are formed by reactions of DMAP-coordinated monomeric Group 13/15 compounds [(dmap)Me_2M-E(SiMe_3)_2] with the transition metal complexes [(Me_3N)Cr(CO)_5], [Fe_3(CO)_(12)], and [Ni(CO)_4]. For the first time, this reaction offers a general pathway to compounds containing a Group 13 metal and a transition metal bridged by a pentel atom. Complexes prepared in this way were characterized by IR and multinuclear NMR spectroscopy and by single-crystal X-ray structure analysis. Their elecronic and structuela properties are discussed in detail. The Group 13/15 ligands are very weak #pi# acceptors, which is likely to be due to the elecropositive Group 13 metal, and the complexes feature comparatively long pentel-transition metal bonds. In addition, the synthesis and structual charactrization of the parent DMAP-coordianted gallanes [(dmap)-Me_2Ga-E(SiMe_3)_2] (E=P, As) are reported.