The TpZn–OH/CS2 reaction: theoretical and preparative visualization of an essential bioinorganic reaction path

Abstract

The reaction between L₃Zn–OH complexes (L = N₃ based ligand) and CS₂ which is an analogue of the carbonic anhydrase functionality was computed at the B3LYP/6-311 + G* level to proceed via stable four-center intermediates [L₃Zn–SC(S)OH or L₃Zn–SC(O)SH] to give L₃Zn–SH and COS; in agreement with these calculations, the chemical reaction of Tp^Ph,MeZn–OH with CS₂ resulted in the quantitative formation of Tp^Ph,MeZn–SH and COS; in the presence of 1 equivalent of MeOH the reaction yielded Tp^Ph,MeZn–SC(S)OMe, thus also supporting the existence of the four-center intermediate L₃Zn–SC(S)OH.