10. "Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex," Igor V. Kourkine and David S. Glueck, Inorganic Chemistry 1997, 36, 5160-5164.
The dimeric platinum phosphinidene complex [Pt(dppe)(µ-PMes)]2 (1, dppe = Ph2PCH2CH2PPh 2, Mes = 2,4,6-Me3C6H2) was prepared by double deprotonation of [Pt(dppe)(µ-PHMes)]2[BF4] 2 (3); use of one equiv of base gives the monocation [{Pt(dppe)}2(µ-PHMes)(µ-PMes)][BF4] (2), which can also be made from 1 and one equiv of HBF4. NMR data suggest that complex 1 contains pyramidal µ-phosphinidene ligands, and it undergoes nucleophilic reactions typical of a tertiary phosphine. Alkylation with MeI affords [Pt(dppe){µ-P(Me)Mes}]2[BF4]2 (4), BH3€THF gives the borane adduct [Pt(dppe){µ-P(BH3)Mes}]2 (5), and air oxidation yields [Pt(dppe){µ-P(O)Mes}]2 (6). However, reaction with sulfur gives the monomeric trithioxophosphorane complex Pt(dppe)(S3PMes) (7), which was prepared independently from Pt(dppe)(trans-stilbene) and [MesPS2] 2.