Abstract
Facile ligand substitution is observed when the ruthenium azido complex (PPh3)[Ru]-N3 (1; [Ru] = Tp(PPh3)Ru) is treated with CH3CN, yielding the nitrile-substituted ruthenium azido complex (CH3CN)[Ru]-N3 (2). Alkylation, [3 + 2] cycloaddition, and catalytic reactions of complex 2 have been investigated. In the case of [3 + 2] cycloaddition reactions, the metal-bound heterocyclic complexes (CH3CN)[Ru]-N3C2(CO2Me)2 (3a), (CH3CN)[Ru]-N3C2HCO2Me (5), and (CH3CN)[Ru]-N3C2HCN (6) are obtained from dimethyl acetylenedicarboxylate, methyl propiolate, and fumaronitrile, respectively. The tetrazolato complex [(CN)2C═C(CN)2][Ru]-N4C[C(CN)═C(CN)2] (8) is prepared from 2 and TCNE. Alkylation of 3a with organic bromides affords N-alkylated five-membered-ring organic triazoles. The reaction of CS2 with 2 produces the thermally unstable thiothiatriazolate (CH3CN)[Ru]-N3CS(S) (10), which decomposes to the isothiocyanate (CH3CN)[Ru]-NCS (11). On the other hand, several cationic imine complexes {(CH3CN)[Ru]-(NH═CHR)}+ (12a,...
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