Synthesis of arene ruthenium triazolato complexes by cycloaddition of the corresponding arene ruthenium azido complexes with activated alkynes or with fumaronitrile

The neutral arene ruthenium azido complexes [(eta(6)-p-cymene)Ru(LL)(N-3)], [LL = acetylacetonato (acac) (4), benzoylacetonato (bzac) (5) diphenylbenzoyl methane (dbzm) (6)] undergo [3+2] cycloaddition reaction with a series of activated alkynes and fumaronitrile to produce the arene ruthenium triazolato complexes: [(eta(6)-p-cymene)Ru(LL)[N3C2(CO2R)(2)]] [LL = (acac), R = Me (7); LL = (bzac), R = Me (8); LL = (dbzm), R Me (9); LL = (acac), R = Et (10); LL = (bzac), R = Et (11); LL = (dbzm), R = Et (12) and [(eta(6)-p-cymene)Ru(LL)(N3C2HCN)]; LL acac (13), bzae (14); dbzm (15). However, cationic azido complexes, [(eta(6)-p-cymene)Ru(dppe)(N-3)](+) and [(eta(6)-p-cymene)Ru(dppm)(N-3)](+) do not undergo such cycloaddition reactions. The complexes were characterized on the basis of microanalyses, FT-IR and NMR spectroscopic data. Crystal structures of representative complexes were determined by single crystal X-ray diffraction. (c) 2006 Elsevier B.V. All rights reserved.