Zr−E π-Bonding in Complexes Derived from E−H Additions to Cp2Zr(P(C6H2-2,4,6-t-Bu3))(PMe3)

Additions of PhEH (E = O, S), PhEH 2 (E = N, P), MesPH 2, and Ph 2 PH to Cp 2 Zr(PR*)(PMe 3 ) ( 2 ) provide a facile route to complexes of the form Cp 2 Zr(PHR*)(ER) (R* = 2,4,6- t -Bu-C 6 H 2; ER = OPh ( 3 ), SPh ( 4 ), NHPh ( 5 ), PHPh ( 6 ), PHMes ( 7 ), PPh 2 ( 8 )). Variable-temperature NMR studies are consistent with facile metal-mediated inversion at phosphorus as well as rapid rotation about the Zr−E bonds at room temperature.