Carbonyl complexes of ruthenium(II) with unsymmetrical phosphinephosphinesulfide ligands of the type Ph₂P(CH₂)_πP(S)Ph₂, π=14

Reaction of [Ru(CO)(2)Cl-2](n) with ligands Ph2P(CH2)(n) P(S)Ph-2 (n = 1(a), 2(b), 3(c), 4(d)) in 1:1 molar ratio produces complex cis-[Ru(CO)(2)Cl-2(P boolean AND S)](1a) (P boolean AND S = eta(2)-(P, S) Coordinated) and cis -[Ru(CO)(2)Cl-2(P-S)](1b-d) (P-S = eta(1)-(P) coordinated), while 1:2 molar ratio yields complex of the type cis -[Ru(CO)(2)Cl-2(P-S)(2)](2a-d). The complex 2a undergoes partial decarbonylation reaction in CH2Cl2-hexane solution to give a new chelated complex [Ru(CO)Cl(P boolean AND S)(2)]Cl(2a'). Abstraction of halide with AglO(4) from the non-chelated complexes 1b-d and 2a-d afford corresponding chelated complexes [Ru(CO)(2)Cl(P boolean AND S)](ClO4)(3b-d) and [Ru(CO)(2)(P boolean AND S)(2)](ClO4)(2)(4a-d). The molecular structure of the complex 2a' has been determined by single crystal X-ray diffraction. The ruthenium atom is at the Centre of slightly distorted octahedral structure having the two phosphorus atoms of the two chelated P, S coordinated ligands at trans to each other, one CO group and Cl atom completing the coordination sphere. Other complexes have been characterized by elemental analysis, IR, 1H and 31p JHJ NMR spectroscopy. (C) 2003 Elsevier Ltd. All rights reserved.