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

Abstract

The heterobimetallic bismuth-oxo-bridged complexes containing the Bi-O-M (M = Al, Ga, Ge, Zr, Hf) core were prepared. The reaction of L(1)BiNMe(2) (1) [L(1) = 1,8-C(10)H(6)(NSiMe(3))(2)] with LM-(Me)(OH) and LGe(OH) (M = Al, Ga, L = CH((CMe)NAr)(2), Ar 2,6-iPr(2)C(6)H(3)) proceeds via HNMe(2) elimination and provides the complexes L(1)Bi(mu-O)MMeL(M = Al2; Ga, 3) and L(1)Bi(mu-O)-GeL (4). The transition metal hydroxides Cp (2)ZrMe(OH) and Cp (2)HfCl(OH) react with 1 in n-hexane and toluene, respectively, under elimination of 1 equiv of HNMe(2) to generate the corresponding complexes L(1)Bi(mu-O)ZrMeCp (2) (5) and L(1)Bi(mu-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 P2(1)/c and P2(1)/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.