Tungsten phosphanylarylthiolato complexes [W{PhP(2-SC6H4)2-κ3S,S′,P}2] and [W{P(2-SC6H4)3-κ4S,S′,S″,P}2]: Synthesis, structures and redox chemistry

Abstract

PhP(2-SHC₆H₄)₂ (PS₂H₂) reacts with WCl₆ with reduction of tungsten to give the air-sensitive tungsten(IV) complex [W{PhP(2-SC₆H₄)₂-κ³S,S′,P}₂] (1). 1 is oxidised in air to [WO{PhPO(2-SC₆H₄)₂-κ³S,S′,O}{PhP(2-SC₆H₄)₂-κ³S,S′,P}] (2). The attempted synthesis of 2 by reaction of 1 with iodosobenzene as oxidising agent was unsuccessful. [W{P(2-SC₆H₄)₃-κ⁴S,S′,S″,P}₂] (3) was formed in the reaction of P(2-SHC₆H₄)₃ (PS₃H₃) with WCl₆. The W^VI complex 3 contains two PS₃³⁻ ligands, each coordinated in a tetradentate fashion resulting in a tungsten coordination number of eight. The reaction of 3 with AgBF₄ yields the dinuclear tungsten complex [W₂{P(2-SC₆H₄)₃-κ⁴S,S′,S″,P}₃]BF₄ (4). Complexes 1–4 were characterised by spectral methods and X-ray structure determination.