INTRAMOLECULAR REDOX REACTIONS IN THERMAL REDUCTION OF ADDITION COMPLEXES OF TYPE MO(NO)2CL2L2 AND MO(NO)CL3L2

The intermediates formed from Mo(NO) 2 Cl 2 L 2 and Mo(NO)Cl 3 L 2 by splitting-off of weakly-coordinated ligands L (alcohols, glycols, nitriles) decompose in exothermic reactions: the decomposition products are N 2 , MoOCl 4 and MoO 3 . If the ligand L is strongly coordinated and is reducing (DMFA, DMSO, Pph 3 , Asph 3 ), the NO groups oxidize the ligand L by formation of N 2 in an exothermic intramolecular redox process under 300‡. The central atom is oxidized by NO, and N 2 O is formed above 300‡ in the case of non-reducing ligands L (OPph 3 , OAsph 3 ). An endothermic redox reaction with chlorine formation is observed during decomposition of the trichloro complex. The solid residue is metallic molybdenum. © 1979 Wiley Heyden Ltd., Chichester and Akadémiai Kiadó, Budapest.