As eries of W IV alkyne complexes with the sulfurrich ligand hydridotris(2-mercapto-1-methylimidazolyl) borate)(Tm Me)a re presented as bio-inspired modelst oe lucidate the mechanism of the tungstoenzyme acetylene hydratase (AH). The mono-a nd/or bis-alkyne precursors were reacted with NaTm Me and the resulting complexes [W(CO)(C 2 R 2)(Tm Me)Br] (R = H 1,M e2)o xidizedt ot he target [WE(C 2 R 2)(Tm Me)Br] (E = O, R = H 4,M e5;E= S, R = H 6,M e7) using pyridine-N-oxidea nd methylthiirane. Halide abstraction with TlOTf in MeCN gave the cationic complexes [WE(C 2 R 2)(MeCN)(Tm Me)](OTf) (E = CO, R = H 10,M e11;E= O, R = H 12,M e13;E= S, R = H 14,M e15). Without MeCN, dinuclearc omplexes [W 2 O(m-O)(C 2 Me 2) 2 (Tm Me) 2 ](OTf) 2 (8)a nd [W 2 (m-S) 2 (C 2 Me 2)(Tm Me) 2 ](OTf) 2 (9)c ould be isolated showing distinct differences between the oxido and sulfido system with the latter exhibiting only one molecule of C 2 Me 2 .T his provides evidencet hat af ine balanceo ft he softnessa tWis important for acetylene coordination.U pon dissolving complex 8 in acetonitrile complex 13 is reconstituted in contrast to 9.All complexes exhibit the desired stability toward water and the observed effective coordination of the scorpionate liganda voidsd ecomposition to disulfide, an often-occurring reactioni ns ulfur ligand chemistry.H ence, the data presented here point towardamechanism with ad irect coordination of acetylene in the active site and provide the basis for further model chemistry for acetyleneh ydratase.