1,2-Silyl Migration in a Novel η²-Phosphasilene-Pt Complex

Transition metal complexes with η²-alkene and η²-alkyne ligands, including those of C=N, C≡N, C=P, C≡P, have been extensively studied due to their catalytic activity and interesting bonding characteristics.¹

While several η² complexes of heavy alkene and alkyne analogues are known, there are only few examples of heavy heteroalkene-transition metal complexes.² We report the synthesis and the X-ray crystallography structures of a novel η²-phosphasilene-Pt(0) complex 1 and its isomer 3.

Thermally induced LiF elimination from lithium phosphide 2 in the presence of L_nPt(0) yields complex 1. In the presence of LDA 1 undergoes quantitatively an unusual 1,2-silyl shift in the coordination sphere of platinum to yield 3. The mechanism of the 1->3 rearrangement and some reactions of 1 and 3, as well as the structures of 1 and 3 will be discussed.

(1) Abel, E. W.; Stone, F. G. A.

(2) Ishida, S.; Iwamoto, T. Coord. Chem. Rev. 2016, 314, 34.