INSERTION OF GECL2 INTO MOLYBDENUM-HYDROGEN BONDS - A CONVENIENT ROUTE TO DICHLOROGERMYL COMPLEXES

Insertion of GeCl2 into the molybdenum-hydrogen bond of CpMo(CO)(3)H ( 1) affords the dichlorogermyl complex CpMo(CO)(3)GeCl2H (2). Complex 2 reacts with PMe3 to give trans-CpMo(CO)(2)(PMe3)GeCl2H (5). The mecha nism of this ligand exchange reaction involving GeCl2 extrusion and in sertion steps is described. Insertion of GeCl2 into the molybdenum-hyd rogen bond of cis/trans-CpMo(CO)(2)(PMe3)H (4) offers an alternative r oute to complex 5. The dichlorogermyl complexes 2 and 5 are slowly chl orinated by CH2Cl2 to give the trichlorogermyl complexes CpMo(CO)(3)Ge Cl3 (3) and trans-CpMo(CO)(2)(PMe3)GeCl3 (6), respectively. Chlorinati on of the dichlorogermyl complexes occurs also with GeCl2(dioxane) in toluene. The crystal structure of 5 is described. (C) 1997 Elsevier Sc ience S.A.