One-pot reactions Of [MCl2(cod)] (cod = cyclo-octa-1,5-diene; M = Pt, Pd) with two equiv of PPh3 or AsPh3, one equiv of thiosalicylic acid, and an excess of triethylamine base, followed by the addition of excess Na[BPh4] to the hot reaction mixture gives complexes [(Ph3E)(2)M(SC6H4CO2)...HNEt3](+)[BPh4](-) (E=P, As). Analogous pyridinium and platinum-thioglycolate [(Ph3P)(2)Pt(SCH2CO2)] derivatives were also prepared. An X-ray crystal structure determination on [(Ph3P)(2)Pt(SC6H4CO2)...HNEt3](+)[BPh4](-) reveals hydrogen-bonding between the NH proton and the carbonyl group of the thiosalicylate ligand, the major effect of which is to flatten the platinum-thiosalicylate moiety. NMR spectroscopic data indicate that the hydrogen-bonding interaction persists in solution. (C) 2002 Elsevier Science B.V. All rights reserved.