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

Article abstract of DOI:10.1021/ic1006082

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.