Tricarbonyldichloro(thiocarbonyl)ruthenium(II) and related complexes: synthesis and réactions to give aminomercaptocarbene and isocyanide complexes

Abstract

Thiocarbonyl chloride reacts with [Ru₃(CO)₁₂] in refluxing heptane solution giving [Ru(CO)₃(CS)Cl₂](1). Reaction of (1) with PPh₃ affords [Ru(CO)₂(CS)Cl₂(PPh₃)](2); the cationic complex [Ru(CO)₂(CS)(CNC₆H₁₁)₂Cl]⁺ is obtained by treating (1) with C₆H₁₁NC. A mixture of species has been obtained from the reaction of (1) with the bidentate ligands Ph₂EC₂H₄EPh₂(E = P or As); only [Ru(Ph₂AsC₂H₄AsPh₂)(CO)₂(CS)Cl][BPh₄] has been isolated in a pure form. Isocyanide complexes of the type [Ru(CNR)(CO)₂Cl₂L](L = CO or PPh₃; R = Ph, C₆H₄Me-p, C₆H₄OMe-p, or C₆H₁₁) have been obtained from the reaction of (1) and (2) with primary amines NRH₂. The ¹H n.m.r. and i.r. spectra of these species are discussed.