N-(1,10-菲咯啉-2-基)咪唑啉亚基钌(II)配合物的合成、结构和性质。

Synthesis, structures, and properties of ruthenium(II) complexes of N-(1,10-phenanthrolin-2-yl)imidazolylidenes.

机构信息

Department of Chemistry, Zhejiang University, Xixi Campus, Hangzhou, 310028, P. R. China.

出版信息

Dalton Trans. 2012 Jan 21;41(3):962-70. doi: 10.1039/c1dt11269d. Epub 2011 Nov 17.

PMID:22089031

Abstract

Mononuclear ruthenium complexes RuCl(L1)(CH(3)CN)(2) (2a), RuCl(L2)(CH(3)CN)(2) (2b), Ru(L1)(CH(3)CN)(3)(2) (4a), Ru(L2)(CH(3)CN)(3)(2) (4b), Ru(L2)(2)(2) (5), RuCl(L1)(CH(3)CN)(PPh(3)) (6), RuCl(L1)(CO)(2) (7), and RuCl(L1)(CO)(PPh(3)) (8), and a tetranuclear complex Ru(2)Ag(2)Cl(2)(L1)(2)(CH(3)CN)(6)(4) (3) containing 3-(1,10-phenanthrolin-2-yl)-1-(pyridin-2-ylmethyl)imidazolylidene (L1) and 3-butyl-1-(1,10-phenanthrolin-2-yl)imidazolylidene (L2) have been prepared and fully characterized by NMR, ESI-MS, UV-vis spectroscopy, and X-ray crystallography. Both L1 and L2 act as pincer NNC donors coordinated to ruthenium (II) ion. In 3, the Ru(II) and Ag(I) ions are linked by two bridging Cl(-) through a rhomboid Ag(2)Cl(2) ring with two Ru(II) extending to above and down the plane. Complexes 2-8 show absorption maximum over the 354-428 nm blueshifted compared to Ru(bpy)(3)(2+) due to strong σ-donating and weak π-acceptor properties of NHC ligands. Electrochemical studies show Ru(II)/Ru(III) couples over 0.578-1.274 V.

摘要

单核钌配合物 RuCl(L1)(CH(3)CN)(2)(2a)、RuCl(L2)(CH(3)CN)(2)(2b)、Ru(L1)(CH(3)CN)(3)(2)(4a)、Ru(L2)(CH(3)CN)(3)(2)(4b)、Ru(L2)(2)(2)(5)、RuCl(L1)(CH(3)CN)(PPh(3))(6)、RuCl(L1)(CO)(2)(7) 和 RuCl(L1)(CO)(PPh(3))(8) 以及一个四核配合物 Ru(2)Ag(2)Cl(2)(L1)(2)(CH(3)CN)(6)(4)(3)，其中含有 3-(1,10-菲咯啉-2-基)-1-(吡啶-2-基甲基)咪唑啉基 (L1) 和 3-丁基-1-(1,10-菲咯啉-2-基)咪唑啉基 (L2)，已通过 NMR、ESI-MS、UV-vis 光谱和 X 射线晶体学进行了全面表征。L1 和 L2 均作为 pincer NNC 供体与钌 (II) 离子配位。在 3 中，Ru(II)和 Ag(I)离子通过菱形 Ag(2)Cl(2)环连接两个桥接 Cl(-)，两个 Ru(II)延伸到平面上方和下方。与 Ru(bpy)(3)(2+)相比，配合物 2-8 在 354-428nm 处的吸收最大值蓝移，这是由于 NHC 配体具有较强的 σ-给体和较弱的 π-受体性质。电化学研究表明，Ru(II)/Ru(III) 偶对在 0.578-1.274V 之间。