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.

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