Synthesis and Structural Characterization of Heterobimetallic Bismuth Complexes with Main Group and Transition Metals

The heterobimetallic bismuth-oxo-bridged complexes containing the Bi−O−M (M = Al, Ga, Ge, Zr, Hf) core were prepared. The reaction of L1BiNMe2 (1) [L1 = 1,8-C10H6(NSiMe3)2] with LM(Me)(OH) and LGe(OH) (M = Al, Ga, L = CH((CMe)NAr)2, Ar = 2,6-iPr2C6H3) proceeds via HNMe2 elimination and provides the complexes L1Bi(μ-O)MMeL (M = Al 2; Ga, 3) and L1Bi(μ-O)GeL (4). The transition metal hydroxides Cp*2ZrMe(OH) and Cp*2HfCl(OH) react with 1 in n-hexane and toluene, respectively, under elimination of 1 equiv of HNMe2 to generate the corresponding complexes L1Bi(μ-O)ZrMeCp*2 (5) and L1Bi(μ-O)HfClCp*2 (6). Compounds 3, 4, and 6 represent the first examples of structurally characterized heterobimetallic complexes featuring the Bi−O−Ga, Bi−O−Ge, and Bi−O−Hf moiety, respectively. The crystal structural data show that the complexes 3 and 4 crystallize in the monoclinic space group P21/c and P21/n, while the complexes 5 and 6 are present in the monoclinic space group Pn. Moreover all compounds have been characterized by element analysis, electron impact mass spectrometry, and NMR spectroscopy.