Synthesis of ruthenium triazolato complexes by the [3+2] cycloaddition of a ruthenium azido complex with acetylacetylenes

摘要

The [3 + 2] cycloaddition of two acetylacetylenes with ruthenium azido complex [Ru] - N-3 (1, [Ru] = (eta(5)-C5H5) (dppe) Ru, dppe = Ph2PCH2CH2PPh2) is reported. The metal-bound heterocyclic complexes produced are triazolato complexes [Ru]N3C2H(COCH3) (2) and [Ru]N3C2(Ph)(COCH3) (3) from 3-butyn-2-one and 4-phenyl-3butyn-2-one, respectively. Both of the structures of 2 and 3 are clearly established as N(2)-bound. Alkylation of 2 with organic halides affords a series of N(1)-bound N(3)-alkyl-4-acetyl triazolato complexes {[Ru]N-3(CH2R)C2H (COCH3)}[X] (4a, R = H, X = I; 4b, R = C6F5, X = Br; 4c, R = Ph, X = Br; 4d, R = 2,6-F-2-C6H3, X = Br; 4e, R = 4-CN-C6H4, X = Br). Treatment of 4a with CH3I in refluxing CHCl3 afforded [Ru]-I (5). The structures of complexes 2, 3, 4a and 5 have been determined by single-crystal X-ray diffraction analysis.