Synthesis of Nitrosylruthenium Complexes Containing 2,2‘:6‘,2‘ ‘-Terpyridine by Reactions of Alkoxo Complexes with Acids

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.

含2,2':6',2''-三联吡啶（2,2':6',2''-terpyridine，简称terpy）的亚硝酰钌配合物已被合成并完成表征。
本研究合成了三种烷氧基配合物：trans-(NO, OCH3), cis-(Cl, OCH3)-[RuCl(OCH3)(NO)(terpy)]PF6（记为[2]PF6）、trans-(NO, OC2H5), cis-(Cl, OC2H5)-[RuCl(OC2H5)(NO)(terpy)]PF6（记为[3]PF6）以及[RuCl(OC3H7)(NO)(terpy)]PF6（记为[4]PF6），三者分别由trans-(Cl, Cl), cis-(NO, Cl)-[RuCl2(NO)(terpy)]PF6（记为[1]PF6）与甲醇钠在甲醇、乙醇及正丙醇中反应制得。
[3]PF6与盐酸、三氟甲磺酸等酸类反应时，其烷氧基配体发生取代，生成对应的亚硝酰配合物。在盐酸溶液中，[3]PF6经反应得到[1]PF6的几何异构体trans-(NO, Cl), cis-(Cl, Cl)-[RuCl2(NO)(terpy)]PF6（记为[5]PF6）。在回流条件下，[3]PF6与三氟甲磺酸在乙腈中反应，得到trans-(NO, Cl), cis-(CH3CN, Cl)-[RuCl(CH3CN)(NO)(terpy)]²+（记为[6]²+）。
经X射线晶体衍射分析，确定了[3]PF6、[4]PF6·CH3CN、[5]CF3SO3及[6](PF6)2的晶体结构。