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Dinuclear ruthenium complexes containing tripodal dithiophosphonate ligands

Authors:	Qing Ma Xi-Ying Wang Wa-Hung Leung

Institution:	^a Department of Applied Chemistry, School of Petrochemical Engineering, Changzhou University, Jiangsu 213164, PR China ^b Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma’anshan, Anhui 243002, PR China ^c Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, PR China

Abstract:	Treatment of (η⁶-p-cymene)RuCl(μ-Cl)]₂ with Lawesson’s reagent ArP(S)(μ-S)]₂ (Ar = p-C₆H₄OMe) in the presence of ammonium hydroxide afforded the dinuclear complex (η⁶-p-cymene)Ru{μ-η¹(S),η²(S,S′)-ArP(O)S₂}]₂ (1) in which the tripodal ArP(O)S₂]²⁻ ligands bind to the ruthenium atom in both bridging and chelating modes with two non-coordinating PO groups. Interaction of RuHCl(CO)(PPh₃)₃] with ArP(S)(μ-S)]₂ and bis(diphenylphosphino)methane (dppm) in the presence of ammonium hydroxide gave the dinuclear complex Ru(CO){μ₃-η¹(O),η²(S,S′)-ArP(O)S₂}(dppm)]₂ (2) in which the tripodal ArPOS₂]²⁻ ligands bind the two Ru atoms via both sulfur and oxygen atoms. Treatment of Ru(PPh₃)₃Cl₂] with ArP(S)(μ-S)]₂ at reflux in the presence of ammonium hydroxide led to the formation of the dinuclear mixed valence complex Ru₂Cl₂(μ-S){μ₃-η¹(O),η¹(S),-η²(S,S′)-ArP(O)S₂}(PPh₃)₃] (3), which contains a Ru^II(PPh₃)₂Cl]⁺ and Ru^IV(PPh₃)Cl]³⁺ moieties by the tripodal ArPOS₂]²⁻ ligand in a μ₃-η¹(O),η¹(S),η²(S,S′) coordination mode and the μ-S²⁻ anion. The crystal structures of 1, 2, and 3·CH₂Cl₂ along with their spectroscopic and electrochemical properties are reported.

Keywords:	Ruthenium Dithiophosphonate Tripodal ligand Synthesis Crystal structure Electrochemistry
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