Co-ordinatively unsaturated ruthenium complexes as efficient alkyne-azide cycloaddition catalysts: Scope and mechanistic evidence

摘要

The performance of 16-electron ruthenium complexes with the general\udformula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or\udOCH2CF3) was explored in azide−alkyne cycloaddition reactions that afford the 1,2,3-\udtriazole products. The scope of the Cp*Ru(PiPr3)Cl precatalyst was investigated for\udterminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic\udstudies were conducted and revealed a number of proposed intermediates. Cp*Ru-\ud(PiPr3)(η2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at\udtemperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex,\udCp*Ru(κ2-iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction\udstructure was obtained. DFT calculations describe a complete map of the catalytic\udreactivity with phenylacetylene and/or benzylazide.