Department of Chemistry and Biochemistry, North Dakota State University, PO Box 6050, Fargo, ND 58108-6050, USA.
Dalton Trans. 2018 Jul 24;47(29):9701-9708. doi: 10.1039/c8dt02260g.
[Ru(tpy)(pyalk)Cl]Cl (pyalk = 2-(2'-pyridyl)-2-propanol) was synthesized and characterized crystallographically and electrochemically. Upon dissolution in water and acetonitrile, [Ru(tpy)(pyalk)Cl]Cl was found to form [Ru(tpy)(pyalk)Cl]+ and [Ru(tpy)(pyalk)(OH)]+, respectively. The Ru(ii/iii) couple of [Ru(tpy)(pyalk)Cl]+ was found to be relatively low compared to that of other Ru complexes in acetonitrile, but the Ru(iii/iv) couple was not significantly different than other Ru complexes bearing anionic ligands. Pourbaix diagrams were generated for [Ru(tpy)(phpy)(OH2)]+ (phpy = 2-phenylpyridine) and [Ru(tpy)(pyalk)(OH)]+ in water, and it was found that [Ru(tpy)(pyalk)(OH)]+ has a lower Ru(ii/iii) potential than [Ru(tpy)(phpy)(OH2)]+ under neutral to alkaline pH. [Ru(tpy)(pyalk)(OH)]+ was found to catalyze C-H bond hydroxylation of secondary alkanes and epoxidation of alkenes using cerium(iv) ammonium nitrate as the primary oxidant.
[Ru(tpy)(pyalk)Cl]Cl（pyalk=2-(2'-吡啶基)-2-丙醇）通过合成和晶体化学及电化学特性进行了表征。在水和乙腈中溶解时，[Ru(tpy)(pyalk)Cl]Cl 分别形成 [Ru(tpy)(pyalk)Cl]+和[Ru(tpy)(pyalk)(OH)]+。与乙腈中的其他 Ru 配合物相比，[Ru(tpy)(pyalk)Cl]+中的 Ru(ii/iii)对相对较低，但 Ru(iii/iv)对与带有阴离子配体的其他 Ru 配合物没有明显差异。在水中生成了[Ru(tpy)(phpy)(OH2)]+（phpy=2-苯基吡啶）和[Ru(tpy)(pyalk)(OH)]+的 Pourbaix 图，发现在中性至碱性 pH 下，[Ru(tpy)(pyalk)(OH)]+的 Ru(ii/iii)电势比[Ru(tpy)(phpy)(OH2)]+低。发现[Ru(tpy)(pyalk)(OH)]+可以使用硝酸铈(IV)铵作为主要氧化剂，催化仲烷的 C-H 键羟化和烯烃的环氧化。
