ABSTRACT: New square-pyramidal bis(ene-1,2-dithiolate)MoSe complexes, [Mo(IV)Se(L)(2)](2-), have been synthesised along with their terminal sulfido analogues, [Mo(IV)S(L)(2)](2-), using alkyl (L(C(4)H(8))), phenyl (L(Ph)) and methyl carboxylate (L(COOMe)) substituted dithiolene ligands (L). These complexes now complete three sets of Mo(IV)O, Mo(IV)S and Mo(IV)Se species that are coordinated with identical ene-1,2-dithiolate ligands. The [alkyl substituted Mo(S/Se)(L(C(4)H(8)))(2)](2-) complexes were reported in prior investigations (H. Sugimoto, T. Sakurai, H. Miyake, K. Tanaka and H. Tsukube, Inorg. Chem. 2005, 44, 6927, H. Tano, R. Tajima, H. Miyake, S. Itoh and H. Sugimoto, Inorg. Chem. 2008, 47, 7465). The new series of complexes enable a systematic investigation of terminal chalcogenido and sup