Synthesis, Characterization and Crystal Structures of Zwitterionic Triazolato Complexes by Reaction of a Ruthenium Azido Complex with Excess Ethyl Propiolate
The synthesis and structures of two novel zwitterionic ruthenium triazolato complexes are reported. The treatment of the ruthenium azido complex [Ru]?N3 (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with an excess of ethyl propiolate in CHCl3 or CH2Cl2 under ambient conditions for 15 days results in the formation of a mixture of the Z- and E-forms of N(1)-bound ruthenium 3-ethylacryl-4-carboxylate-3H-1,2,3-triazolato complexes [Ru]N3(CH=CHCO2Et)C2H(CO2) (Z-3) and (E-3) in a ratio of ca. 5:2. The structures of E-3 and Z-3 were confirmed by single-crystal X-ray diffraction analysis and fully characterized by 1H, 31P, 13C NMR and IR spectroscopy, mass spectrometry, and elemental analysis. The negatively charged carboxylate moieties of the zwitterionic ruthenium triazolato complexes Z-3 and E-3 are highly nucleophilic and reactive toward a variety of electrophiles, making Z-3 and E-3 potential starting materials for the development of biologically active 1,2,3-triazole derivatives.
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