Abstract The 1-alkyne-1-thiolates R-C ≡C-SLi [1a: R = C(CH3)3, 1b: R = C6H11 ] react with L2PtCl2 (L = PPh3, 1/2 dppe) and CpRu(PPh3)2Cl, respectively to give the complexes trans-(Ph3P)2Pt[S-C ≡C-C(CH3)3]2 (2a), cis-dppePt[S-C≡C-C(CH3)3]2 (2b), and CpRu(PPh3)2-(S-C ≡ C-R) [3a: R = C(CH3)3, 3b: R = C6H11]. 2a has been characterized by 31P CP/MAS NM R spectroscopy and its crystal structure determined by X-ray diffraction.