中孔型双核配合物能否为手性的？：双核β-二酮基钌(III)配合物。

Can a meso-type dinuclear complex be chiral?: dinuclear β-diketonato Ru(III) complexes.

机构信息

Graduated School of Science and Engineering, Ehime University, Matsuyama, Ehime 790-8577, Japan.

出版信息

Dalton Trans. 2012 Jan 21;41(3):747-51. doi: 10.1039/c1dt11133g. Epub 2011 Sep 6.

Abstract

Dinuclear Ru(III) complexes, [Ru(III)(acac)(2)(dabe)Ru(III)(acac)(2)] (acacH = acetylacetone; dabeH(2) = 1, 2-diacetyl-1,2-dibenzoylethane) and [Ru(III)(acac)(2)(tbet)Ru(III)(acac)(2)] (tbetH(2) = 1,1,2,2-tetrabenzoylethane) were synthesized by reacting [Ru(acac)(2)(CH(3)CN)(2)]PF(6) with dabeH(2) and tbetH(2) respectively, in toluene. The X-ray structural analysis of a meso-type dinuclear Ru(III) complex, ΔΛ-[Ru(III)(acac)(2)(dabe)Ru(III)(acac)(2)], showed that the bridging part became chiral due to the orthogonal twisting of two non-symmetrical β-diketonato moieties. To confirm this conclusion, the complex was resolved chromatographically to provide a pair of optical antipodes. Such chirality in the bridging part was not generated for [Ru(III)(acac)(2)(tbet)Ru(III)(acac)(2)], because the β-diketonato moieties in tbet(2-) are symmetrical.

摘要

双核钌(III)配合物，[Ru(III)(acac)(2)(dabe)Ru(III)(acac)(2)]（acacH=乙酰丙酮；dabeH(2)=1,2-二乙酰基-1,2-二苯甲酮）和[Ru(III)(acac)(2)(tbet)Ru(III)(acac)(2)]（tbetH(2)=1,1,2,2-四苯甲酮）分别通过[Ru(acac)(2)(CH(3)CN)(2)]PF(6)与 dabeH(2)和 tbetH(2)在甲苯中的反应合成。一个介体型双核钌(III)配合物，ΔΛ-[Ru(III)(acac)(2)(dabe)Ru(III)(acac)(2)]的 X 射线结构分析表明，由于两个非对称β-二酮酯部分的正交扭曲，桥接部分变得手性。为了证实这一结论，该配合物通过色谱法拆分，得到一对对映异构体。对于[Ru(III)(acac)(2)(tbet)Ru(III)(acac)(2)]，桥接部分不会产生这种手性，因为 tbet(2-)中的β-二酮酯部分是对称的。