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

The reactions of R2PP(SiMe3)Li (R = tBu, iPr2N) with [Cp2MoCl2] yield terminal phosphanylphosphido complexes formally via the insertion of the phosphinidene P-atom into the CH bond of a cyclopentadienyl ring and the migration of the hydrogen atom or SiMe3 moiety to the molybdenum centre. Solid state structures of [Cp(C5H4PPtBu2)MoH], [Cp(C5H4PPtBu2)Mo(SiMe3)] and [Cp{C5H4PP(NiPr2)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.

Graphical abstractR2P–P(SiMe3)Li (R = tBu, iPr2N) reacts with [Cp2MoCl2] yielding a new class of phosphanylphosphido complexes of Mo(IV).Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Syntheses of the first terminal phosphanylphosphido complexes of molybdenum. ► Formation of PC bond via an insertion of phosphido P atom into CH bond of a Cp ring. ► The solid state structures of [Cp(C5H4PPR2)MoX] (R = tBu, iPr2N; X = H, SiMe3).