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Synthesis of nitrosylruthenium complexes containing 2,2':6',2"-terpyridine by reactions of alkoxo complexes with acids
Authors:Nagao Hirotaka  Enomoto Keiji  Wakabayashi Yuuki  Komiya Gen  Hirano Toshiyuki  Oi Takao
Affiliation:Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo 102-8554, Japan. h-nagao@sophia.ac.jp
Abstract:Nitrosylruthenium complexes containing 2,2':6',2"-terpyridine (terpy) have been synthesized and characterized. The three alkoxo complexes trans-(NO, OCH3), cis-(Cl, OCH3)-[RuCl(OCH3)(NO)(terpy)]PF6 ([2]PF6), trans-(NO, OC2H5), cis-(Cl, OC2H5)-[RuCl(OC2H5)(NO)(terpy)]PF6 ([3]PF6), and [RuCl(OC3H7)(NO)(terpy)]PF6 ([4]PF6) were synthesized by reactions of trans-(Cl, Cl), cis-(NO, Cl)-[RuCl2(NO)(terpy)]PF6 ([1]PF6) with NaOCH3 in CH3OH, C2H5OH, and C3H7OH, respectively. Reactions of [3]PF6 with an acid such as hydrochloric acid and trifluoromethansulforic acid afford nitrosyl complexes in which the alkoxo ligand is substituted. The geometrical isomer of [1]PF6, trans-(NO, Cl), cis-(Cl, Cl)-[RuCl2(NO)(terpy)]PF6 ([5]PF6), was obtained by the reaction of [3]PF6 in a hydrochloric acid solution. Reaction of [3]PF6 with trifluoromethansulforic acid in CH3CN gave trans-(NO, Cl), cis-(CH3CN, Cl)-[RuCl(CH3CN)(NO)(terpy)]2+ ([6]2+) under refluxing conditions. The structures of [3]PF6, [4]PF6.CH3CN, [5]CF3SO3, and [6](PF6)2 were determined by X-ray crystallograpy.
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