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

Publication date: Available online 18 May 2019Source: Inorganica Chimica ActaAuthor(s): Chao-Wan Chang, Gene-Hsiang LeeAbstractThe [3+2] cycloaddition of two acetylacetylenes with ruthenium azido complex [Ru]−N3 (1, [Ru] = (η5-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-3-butyn-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]N3(CH2R)C2H(COCH3)}[X] (4a, R = H, X = I; 4b, R = C6F5, X = Br; 4c, R = Ph, X = Br; 4d, R = 2,6-F2-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.Graphical abstract

Source: Inorganica Chimica Acta - May 18, 2019 Category: Chemistry Source Type: research