Solvent-Driven P–S vs P–C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions

Abstract

The outcome of the reaction of the Pt(III),Pt(III) complex [(C6F5)2PtIII(μ-PPh2)2PtIII(C6F5)2](Pt–Pt) (1) with the S-based anions thiophenoxide (PhS–), ethyl xanthogenate (EtOCS2–), 2-mercaptopyrimidinate (pymS–), and 2-mercaptopyridinate (pyS–) was found to be dependent on the reaction solvent. The reactions carried out in acetone led to the formation of [NnBu4][(RF)2PtII(μ-PhS-PPh2)(μ-PPh2)PtII(RF)2] (2), [NnBu4][(RF)2PtII(μ-EtOCS2-PPh2)(μ-PPh2)PtII(RF)2] (3), [NnBu4][(RF)2PtII(μ-pymS-PPh2)(μ-PPh2)PtII(RF)2] (4), and [NnBu4][(RF)2PtII(μ-pyS–PPh2)(μ-PPh2)PtII(RF)2] (5), respectively (RF = C6F5). Complexes 2–5 display new Ph2P(SL) ligands exhibiting a κ2-P,S bridging coordination mode, which is derived from a reductive elimination of a PPh2 group and the S-based anion. Carrying out the reaction in dichloromethane afforded, in the cases of EtOCS2– and pymS–, the monobridged complexes [NnBu4][(PPh2RF)(RF)2PtII(μ-PPh2)PtII(EtOCS2)(RF)] (6) and [NnBu4][(PPh2RF)(RF)2PtII(μ-PPh2)PtII(pymS)(RF)] (7), respectivel...