| Summary: | 碩士 === 臺北市立大學 === 應用物理暨化學系 === 107 === The [3+2] cycloaddition reactions of alkynes and alkenes with ruthenium azido complex Tp(PPh3)(NH=CPh2)Ru-N3 (4) have been investigated. Addition of CS2 to 4 produces thermally unstable thiothiatriazolate Tp(PPh3)(NH=CPh2)Ru-N3CS(S), which converts to the linear structure of Tp(PPh3)(NH=CPh2)Ru-NCS (5). The metal-bound heterocyclic complexes the five-membered triazolato and tetrazolato Tp(PPh3)(NH=CPh2)Ru[N3C2(CO2CH3)2] (6), Tp(PPh3)(NH=CPh2)Ru{N4C[C(CN)=C(CN)2]} (9) are obtained from dimethyl acetylene dicarboxylate and tetracyanoethylene, respectively. Reaction of 4 with the haloalkylate benzyl bromide affords the halogenated complex Tp(PPh3)(NH=CPh2)Ru-Br (8). Protonation of complex 6 with excess HCl gives 1,4,5-triazolato complex Tp(PPh3)ClRu[N3HC2(CO2CH3)2] (7). Preliminary results on the catalytic activity of Tp(PPh3)(NH=CPh2)Ru-X (X= Cl; N3) are also presented. Tp(PPh3)(NH=CPh2)Ru-X catalyzes cycloaddition of terminal alkynes and benzyl azide to give the triazoles in organic and aqueous medium. The selective and conversion rate depends on alkyne substrates. The structures of 5, 7, and 8 have been determined by X-ray diffraction analysis.
Keyword : Tp, Ruthenium, Azido, Benzophenone Imine, Catalyst.
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