Thermal and thermally assisted photochemical conversion of [Mo(NO)]3+ to [Mo(NO)]2+ in a ketonic solvent: single-step synthesis of nitrosyl(thiocyanato)molybdenum(I) derivatives from [Mo(NO)(NH2O)(NCS)2(L–L)](L–L = 2,2′-bipyridine or 1,10-phenanthroline)

Abstract

[Mo(NO)(NH₂O)(NCS)₂(phen)](phen = 1,10-phenanthroline) on refluxing in acetophenone or on photolysis at 80 °C affords five-co-ordinated paramagnetic and e.s.r. sensitive [Mo(NO)]²⁺ species, [Mo(NO)(NCS)₂(phen)], the products obtained by the two different routes being isomeric. The i.r. and u.v.–visible spectral data suggest that while the former route affords a trigonal bipyramidal geometry, the latter affords a square pyramidal product. The 2,2′-bipyridine (bipy) analogue on identical photolysis reaction gives the corresponding square pyramidal product like the phen complex, but on reflux with acetophenone it probably forms [Mo₂(NCS)₄(bipy)₂].