Triphosphanato (R3P32−), primary phosphido (RPH−) and diphosphanato (diphosphene) (R2P22−) complexes of zirconium and hafnium metallocenes

Abstract A variety of triphosphanato (R 3 P 3 2− ) primary phosphido (RPH − ) and diphosphanato (diphosphene) (R 2 P 2 2− ) derivatives of zirconium and hafnium ( I–IV ) have been prepared via reactions of primary phosphides LiPH(R) (R = Ph, t -Bu) with Cp 2 MCl 2 (Cp = η 5 -C 5 H 5 , C 5 Me 3 , C 5 H 3 (SiMe 3 ) 2 ). The products depend on the steric bulk of the P R group and the Cp (or substituted Cp) group. When Cp = C 5 H 5 or C 5 Me 5 and R = Ph, triphosphanato complexes of type I are produced (E. Hey, S. G. Bott and J. L. Atwood, Chem. Ber. 1988, 121 , 561). When R = t -Bu, types II and III are also formed. For Cp = C 5 H 3 (SiMe 3 ) 2 diphosphanato complexes IV and the diphosphides III are formed.