Abstract
The dimeric platinum phosphinidene complex [Pt(dppe)(μ-PMes)]2 (1; dppe = Ph2PCH2CH2PPh2, Mes = 2,4,6-Me3C6H2) was prepared by double deprotonation of [Pt(dppe)(μ-PHMes)]2[BF4]2 (3); use of 1 equiv of base gives the monocationic complex [{Pt(dppe)}2(μ-PHMes)(μ-PMes)][BF4] (2), which can also be made from 1 and 1 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.
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