Synthesis and Structures of Oxo-Bridged Distannyl- and Digermyldirhenium Complexes

Abstract

The reaction of Re 2 (CO) 8 (μ-SnPh 2 ) 2 ( 1 ) with NaOMe in methanol in the presence of Bu n 4 NBr yielded the salt [NBu n 4 ][Re 2 (CO) 8 {μ-Ph 2 SnO(Me)SnPh 2 }] ( 3 ). The anion of 3 contains a Ph 2 SnO(Me)SnPh 2 ligand formed by the addition of a [OMe] - group to the two bridging SnPh 2 groups in 1 . The bidentate ligand bridges the two Re(CO) 4 groups that are joined by a Re−Re single bond. The reaction of Re 2 (CO) 8 [μ-C(H)C(H)Bu n ](μ-H) with Ph 3 GeH and H 2 O in heptane solvent yielded the complex Re 2 (CO) 8 [μ-Ph 2 GeO(H)GePh 2 ](μ-H) ( 4 ). The structure of 4 consists of two Re(CO) 4 units bridged by a Ph 2 GeO(H)GePh 2 ligand and a hydrido ligand that bridges the Re−Re bond. Compound 4 was deprotonated at the OH group by treatment with [NBu n 4 ][OH] to give the salt [NBu n 4 ][Re 2 (CO) 8 (μ-Ph 2 GeOGePh 2 )(μ-H)] ([NBu n 4 ]· 5 ). The three new compounds were characterized by IR, 1 H NMR, and single-crystal X-ray diffraction analyses. The electronic structures of 4 and 5 were probed by computations employing density functional theory (ADF 2004.01, PW91).