Synthesis of polymer-bound nitridomolybdenum(VI) complexes as model polymer complexes of nitrogenase: effect of polymer environment in the Hydrolytic formation of ammonia

Polymer-bound nitridomolybdenum(VI) complexes, MoNCl₃(polystyrene-bound bipyridyl) (I), MoNCl₂(bpy)(polystyrene-bound benzylthiolato) (II), and MoNCl (S-t-Bu)(bpy)(polystyrene-bound benzylthiolato) (III), were synthesized by the reaction of MoNCl₃(CH₃CN)_x or MoNCl₃(bpy) with polystyrene-bound bipyridyl or benzylthiol. The polymer-bound nitridomolybdenum complexes were characterized by photo-acoustic and resonance Raman spectra. Hydrolysis or hydrolytic reduction of the nitridomolybdenum(VI) complexes resulted in the formation of ammonia in the following order of yield: III & II & I. Coordination of the polymer thiolato ligands is thus important in enhancing reductive cleavage of the nitridomolybdenum bond.