Study on the transition metal complexes with unstable silicon and germanium ligands

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(1) Silyl(silylene)tungsten and -molybdenum complexes Cp^*M(CO)_2(=SiMes_2)(SiMe_2) (M = Mo, W ; Mes = mesityl) have been synthesized photochemically. Reaction of the molybdenum complex with N,N-dimethylpyridine (DMAP) and nitriles afforded Cp^*Mo(CO)_2(=SiMesMe・DMAP(SiMesMe_2) and Cp^*M(CO)_2(RC=NSiMe_2SiMes_2Me_2), respectively. In contrast to the molybdenum complex, the tungsten complex did not react with DMAP and nitriles under the same reaction conditions. Reaction of the tungsten and molybdenum complexes with isocyanides gave Cp^*M(CO)_2(=Si(Mes)(C(Mes)=NR))(SiMesMe_2).(2) A germyl(germylene)tungsten complex has been synthesized in a good yield. Reaction of the germyl(germylene) complex with Fe(CO)_5 resulted in the migration of germyl group from tungsten to iron atom to form a germylene-bridged iron-tungsten complex.(3) Photo irradiation of a iron complex in the presence of dihydrogerman Mes_2GeH_2 afforded a novel germylene-bridged diiron complex with a triplet ground state.(4) The first silylene complex of early transition metal has been synthesized using methoxydisilane and tantalum complex in a moderate yield. The complex was characterized by crystal structure analysis.