Metal complexes of sulphur ligands. Part 16. Reaction of mer-tri-chlorotris(dimethylphenylphosphine)ruthenium and dichlorotris(tri-phenylphosphine)ruthenium with sodium and ammonium monothio-benzoates, and the crystal and molecular structure of (4-amino-2-imino-4-methylpentane)bis(dimethylphenylphosphine)bis(monothio-benzoato)ruthenium(II)

Abstract

Reaction of [RuCl₂(PPh₃)₃] with an excess of Na[SOCPh] or [NH₄][SOCPh] in either acetone or methanol and mer-[RuCl₃(PMe₂Ph)₃] with Na[SOCPh] in acetone gives six-co-ordinate [Ru(SOCPh)₂(PR₃)₂][PR₃= PPh₃(1) or PMe₂Ph (2)] shown by i.r. and ¹H and ³¹P n.m.r. studies to contain tans- and cis-PR₃ groups respectively. Support for these conclusions comes from the reactions of (1) and (2) with various Lewis bases which give [Ru(SOCPh)₂(PR₃)₂L₂][PR₃= PPh₃, L = CO or NH₃(3a); PR₃= PMe₂Ph, L = CO, NH₃ or NH₂Et (3b)], shown by spectroscopic methods to have trans-S-bonded [SOCPh]- groups with trans-PPh₃, trans-L (3a), and cis-PMe₂ Ph, cis-L (3b) groups respectively. In contrast, reaction of mer-[RuCl₃(PMe₂Ph)₃] with excess of [NH₄]-[ SOCPh] in acetone gives a nitrogen-containing product (4) shown by X-ray analysis to be [Ru(SOCPh)₂-{HNC(Me)CH₂CMe₂NH₂}(PMe₂Ph)₂]. The crystals are orthorhombic, space group Pna2₁ with a= 23.899(2), b= 11.163(1), and c= 13.889(3)Å. Finally, a mechanism of formation of (4) is suggested involving condensation of the diammine complex (3b) with mesityl oxide.