1,3,5-Tris(thiocyanatomethyl)mesitylene as a Ligand. Pseudooctahedral Molybdenum, Manganese, and Rhenium Carbonyl Complexes and Copper and Silver Dimers. Copper-Catalyzed Carbene- and Nitrene-Transfer Reactions

New molybdenum(0), molybdenum(II), manganese(I), rhenium(I), silver(I), and copper(I) complexes with the 1,3,5-tris(thiocyanatomethyl)mesitylene [Ms(CH2SCN)3] ligand have been synthesized and characterized by IR, NMR, and by X-ray diffraction (except for the rhenium complex). The Ms(CH2SCN)3 ligand coordinated with the molybdenum, manganese, and rhenium carbonyl fragments as a tripodal chelate. With copper and silver, dimeric dicationic species were obtained instead, with the Ms(CH2SCN)3 ligand acting simultaneously as a bidentate chelate and bridge. The [{Cu(Ms(CH2SCN)3)}2][BAr′4]2 (BAr′4 = tetra(3,5-bis(trifluoromethyl)phenyl)borate) product is an excellent catalyst for cyclopropanation and aziridination of alkenes and cyclopropenation of alkynes by means of carbene- and nitrene-transfer reactions.