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RESEARCH PRODUCT

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

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Bimetallic, pentel-bridged complexes of the type [(dmap)Me 2 -M-E(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 2 M-E(SiMe 3 ) 2 ] with the transition metal complexes [(Me 3 N)Cr-(CO) 5 ], [Fe 3 (CO) 1 2 ], 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 electronic and structural properties are discussed in detail. The Group 13/15 ligands are very weak π acceptors, which is likely to be due to the electropositive Group 13 metal, and the complexes feature comparatively long pentel-transition metal bonds. In addition, the synthesis and structural characterization of the parent DMAP-coordinated gallanes [(dmap)-Me 2 Ga-E(SiMe 3 ) 2 ] (E = P, As) are reported.