Metal complexes of sulphur ligands. Part 21. Reactions of [Ru(SOCPh)2(PMe2Ph)2] with Ph2P(CH2)nPPh2(n= 1 or 2) and PMe2Ph and of cis-[RuCl2(PMe2Ph)4] with ammonium monothiobenzoate. Crystal and molecular structure of [Ru(SOCPh)2(PMe2Ph){Ph2P(CH2)2PPh2}]·MeOH

Abstract

Whereas reaction of [Ru(SOCPh)₂(PMe₂Ph)₂](1) with Ph₂PCH₂PPh₂(dppm) in ethanol (1 : 1 molar ratio) gives mer-[Ru(SOCPh)₂(PMe₂Ph)₃]–dppm, the corresponding reaction with Ph₂P(CH₂)₂PPh₂(dppe) gives, after recrystallisation from methanol, the product [Ru(SOCPh)₂(PMe₂Ph)(dppe)]·MeOH. This has been shown by ¹H and ³¹P-{¹H} n.m.r. spectroscopy to consist of two isomers (3a) and (3b) with bidentate and S-bonded ^–SCOPh groups and the structure of (3b) has been verified by X-ray analysis. The crystals are triclinic, space group P, with a= 10.01(1), b= 14.70(1), c= 18.52(1)Å, α= 75.2(3), β= 83.6(3), and γ= 73.5(3)°. Reaction of compound (1) with an excess of PMe₂Ph gives an isomeric mixture of mer-[Ru(SOCPh)₂(PMe₂Ph)₃] whereas shaking cis-[RuCl₂(PMe₂Ph)₄] in benzene or methanol for short periods with [NH₄][SOCPh] gives the facial isomer. If cis-[RuCl₂(PMe₂Ph)₄] is shaken with [NH₄][SOCPh] in methanol for several hours, however, the cation [Ru(SOCPh)(PMe₂Ph)₄]⁺ can be isolated by addition of Na[BPh₄].