Synthesis of benzene ruthenium triazolato complexes by [3+2] cycloaddition reactions of activated alkynes and fumaronitrile to benzene ruthenium azido complexes

摘要

The dinuclear complex [(eta(6)-C6H6) Ru(mu-N-3)Cl](2) (1) is obtained by the reaction of [(eta(6)-C6H6)RuCl2](2) with sodium azide in ethanol. The benzene ruthenium beta-diketonato complexes of the general formula [(eta(6)-C6H6)Ru(L boolean AND L)Cl] {L boolean AND L = O,O'-acac (2); O, O'-bzac (3); O, O'-dbzm (4)} are obtained in methanol by the reaction of [(eta(6)-C6H6)RuCl2](2) with the corresponding beta-diketonates. These complexes further react with sodium azide in ethanol to yield complexes of the type [(eta(6)-C6H6)Ru(L boolean AND L)N-3] [L boolean AND L = O,O'-acac (5); L boolean AND L = O, O'-bzac (6); L boolean AND L = O, O'-dbzm (7)]. The complexes 5-7 are obtained as well by treating 1 with sodium salts of beta-diketonates. These neutral benzene ruthenium azido complexes undergo [3+2] dipolar cycloaddition reaction with activated alkynes (MeO2CC CCO2Me, EtO2CC CCO2Et) or fumaronitrile (NCHC CHCN) to yield the corresponding benzene ruthenium triazolato complexes; [(eta(6)-C6H6) Ru(O,O'-acac){N3C2(CO2Me)(2)}] (8), [(eta(6)-C6H6)Ru(O,O'-acac){N3C2(CO2Et)(2)}] (9), [(eta(6)-C6H6)Ru(O,O'-acac){N3C2HCN}] (10), [(eta(6)-C6H6)Ru(O,O'-bzac){N3C2HCN}] (11) and [(eta(6)-C6H6) Ru(O,O'-dbzm){N3C2HCN}] (12). These complexes are fully characterized on the basis of microanalyses, FT-IR and FT-NMR spectroscopy. The molecular structure of [(eta(6)-C6H6)Ru(O,O'-acac){N3C2{CO2C2H5)(2)}] (9) is confirmed by single crystal X-ray diffraction study. (C) 2007 Elsevier B.V. All rights reserved.