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

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.