Syntheses and structures of the first terminal phosphanylphosphido complexes of molybdenum(IV)

The reactions of R2P-P(SiMe3)Li (R = Bu-t, (Pr2N)-Pr-i) with [Cp2MoCl2] yield terminal phosphanylphosphido complexes formally via the insertion of the phosphinidene P-atom into the C-H bond of a cyclopentadienyl ring and the migration of the hydrogen atom or SiMe3 moiety to the molybdenum centre. Solid state structures of [Cp(C5H4P-(PBu2)-Bu-t)MoH], [Cp(C5H4P-(PBu2)-Bu-t)Mo(SiMe3)] and [Cp{C5H4P-P((NPr2)-Pr-i)(2)}Mo(SiMe3)] were established by single crystal X-ray diffraction. The proposed reaction path is supported by the results of NMR studies and DFT calculations. (C) 2012 Elsevier Ltd. All rights reserved.