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Abstract  Bioinspired complexes employing the ligands 6‐ tert ‐butylpyridazine‐3‐thione (SPn) and pyridine‐2‐thione (SPy) were synthesized and fully characterized to mimic the tungstoenzyme acetylene hydratase (AH). The complexes [W(CO)(C 2 H 2 )(CHCH‐SPy)(SPy)] ( 4 ) and [W(CO)(C 2 H 2 )(CHCH‐SPn)(SPn)] ( 5 ) were formed by intramolecular nucleophilic attack of the nitrogen donors of the ligand on the coordinated C 2 H 2  molecule. Labelling experiments using C 2 D 2  with the SPy system revealed the insertion reaction proceeding via a bis‐acetylene intermediate. The starting complex [W(CO)(C 2 H 2 )(SPy) 2 ] ( 6 ) for these studies was accessed by the new acetylene precursor mixture [W(CO)(C 2 H 2 )  n  (MeCN) 3− n  Br 2 ] ( n =1 and 2;  7 ). All complexes represent rare examples in the field of W−C 2 H 2  chemistry with  4  and  5  being the first of their kind. In the ongoing debate on the enzymatic mechanism, the findings support activation of acetylene by the tungsten center.

Structural Mimics of Acetylene Hydratase: Tungsten Complexes Capable of Intramolecular Nucleophilic Attack on Acetylene