Synthesis of indenyl ruthenium triazolato complexes by [3 + 2] cycloaddition of activated nitrile and alkynes to indenyl ruthenium azido complexes: crystal structures of [( η 5-C9H7)Ru(PMe2Ph)2{N3C2(CO2Me)2}] and [( η 5-C9H7)Ru(dppe){N3C2H(CN}

Abstract

The indenyl ruthenium(II) azide complexes [(η5-C9H7)Ru(L2)N3], L2 = (PMe2Ph)2 (1), dppe (2) and dppm (3), (where dppe = Ph2PCH2CH2PPh2 and dppm = PPh2CH2PPh2) were readily prepared by the reaction of NaN3 with corresponding chloro complexes [(η5-C9H7)Ru(L2)Cl]. The azido complexes undergo [3 + 2] dipolar cycloaddition reactions with activated alkynes and nitrile (NCCH = CHCN) to yield new indenyl ruthenium triazolato complexes [(η5-C9H7)Ru(L2)(N3C2(CO2R)2)], L2 = (PMe2Ph)2, R = Me (4), Et (5); L2 = dppe, R = Et (6), L2 = dppm, R = Et (7) and [(η5-C9H7)Ru(L2)(N3C2HCN)], L2 = (PMe2Ph)2 (8), L2 = dppe (9), L2 = dppm (10). The complexes were fully characterized on the basis of microanalyses, IR and NMR spectroscopy. The structures of representative complexes 4 and 9 have been determined by single-crystal X-ray methods.