环金属钌(Ⅱ)亚硝酰配合物的制备及其光化学性质

Preparation and photochemical properties of cyclometalated ruthenium(Ⅱ) nitrosyl complexes

以2-(4-甲基)苯基吡啶为C,N-配体构筑的环金属钌配合物1与NOBF4在不同反应条件下,以较高产率获得了2个环金属钌亚硝酰配合物2和3。温度提高和有氧条件更有利于3的生成。核磁共振谱、质谱、红外光谱及单晶结构显示这2个亚硝酰配合物均具有{Ru^(Ⅱ)-NO^(+)}特征。电化学及紫外可见吸收光谱进一步证实了这一点。随后,对钌亚硝酰配合物2在光照下的产物进行分离并通过NMR和质谱表征,结果表明:此类亚硝酰配合物在光照下断裂Ru—NO并释放NO,金属中心以Ru稳定存在。

Complex 1 with 2-(4-methylphenyl)pyridine as C,N-ligand was used to react with NOBF4 under different conditions to afford two cyclometalated ruthenium􀃭nitrosyl complexes 2 and 3 in high yields.Herein,increasing temperature and aerobic conditions were favored by the generation of 3.NMR,MS,IR,and single-crystal X-ray structure analysis showed that these two nitrosyl complexes have{Ru^(Ⅱ)-NO^(+)}characteristics.This was further confirmed by electrochemistry and UV-Vis absorption spectra.Subsequently,the photolyzed product of ruthenium nitrosyl complex 2 was separated and characterized by NMR and MS spectra.The result showed that such nitrosyl complexes could give a release of NO by the breakage of Ru—NO under the light,along with Ru􀃭as the oxidation state.CCDC:2221223,3.