Low-Temperature “1,2 → 1,7” Isomerization of Sterically Crowded Icosahedral closo-((2,3,8-η3):(5,6-η2)- Norbornadien-2-yl)rhodacarborane via the Formation of a Pseudocloso Intermediate. Molecular Structures of [3,3-((2,3,8-η3):(5,6-η2)-C7H7CH2)-1,2-(4‘-MeC6H4)2- 3,1,2-pseudocloso-RhC2B9H9] and 1,2 →
Low-Temperature “1,2 → 1,7” Isomerization of Sterically Crowded Icosahedral closo-((2,3,8-η3):(5,6-η2)- Norbornadien-2-yl)rhodacarborane via the Formation of a Pseudocloso Intermediate. Molecular Structures of [3,3-((2,3,8-η3):(5,6-η2)-C7H7CH2)-1,2-(4‘-MeC6H4)2- 3,1,2-pseudocloso-RhC2B9H9] and 1,2 →
复制标题
空间拥挤二十面体 closo-((2,3,8-η3):(5,6-η2)- Norbornadien-2-yl)rhodacarborane 的低温“1,2 → 1,7”异构化通过形成[3,3-((2,3,8-η3):(5,6-η2)-C7H7CH2)-1,2-(4-MeC6H4)2- 3,1,2 的拟闭环中间体分子结构。 -pseudocloso-RhC2B9H9] 和 1,2 →
DOI：
--
复制
发表时间：
2005
期刊：
影响因子：
--
通讯作者：
I. Chizhevsky
中科院分区：
文献类型：
--
作者：
A. Safronov;F. M. Dolgushin;P. Petrovskii;I. Chizhevsky
碳硼烷阴离子[7，8-(4‘-MeC6H4)2-7，8-NIDO-C2B9H10]-(1)与[((2，3，5，6-η4)-C7H7-2-CH2OH)RhCl2(2)]2(2)在CHCl3或C6H6溶液中的金属化反应生成两个非对映异构体闭合配合物[2，2-((2，3，8-η3)：(5，6-η2)-C7H7CH2)-1，8-(4‘-MeC6H4)2-2，1，8-closo-RhC2B9H9](5和6)，A(不可分离)[3，3-((2，3，8-(5，6-η2)-C7H7CH2)-1，2-(4‘-MeC6H4)2-3，1，2-closo-RhC2B9H9].)：→3)]的低温“1，2-η1，7”碳原子异构化产物用结晶学方法确定了非对映异构体5和6的整体结构和立体化学结构。确定了异构化反应是通过中间体伪闭合型配合物[3，3-((2，3，8-η3)：(5，6-η2)-C7H7CH2)-1，2-(4‘-MeC6H4)2-3，1，2-pseudocloso-RhC2B9H9](4)进行的，并用微量分析、多核核磁共振光谱和单晶X射线衍射法对其进行了表征。
The metalation reaction of the K+ salt of the carborane anion [7,8-(4‘-MeC6H4)2-7,8-nido-C2B9H10]- (1) with [((2,3,5,6-η4)-C7H7-2-CH2OH)RhCl]2 (2) in a solution of CHCl3 or C6H6 at ambient temperature produced two diastereomeric closo complexes, [2,2-((2,3,8-η3):(5,6-η2)-C7H7CH2)-1,8-(4‘-MeC6H4)2-2,1,8-closo-RhC2B9H9] (5 and 6), the products of the low-temperature “1,2 → 1,7” carbon atom isomerization of a (nonisolable) [3,3-((2,3,8-η3): (5,6-η2)-C7H7CH2)-1,2-(4‘-MeC6H4)2-3,1,2-closo-RhC2B9H9]. The overall architecture and stereochemistry of diastereomers 5 and 6 have been determined crystallographically. It has been established that the isomerization reaction proceeds through the intermediate pseudocloso type complex [3,3-((2,3,8-η3):(5,6-η2)-C7H7CH2)-1,2-(4‘-MeC6H4)2-3,1,2-pseudocloso-RhC2B9H9] (4), which was isolated and characterized by microanalysis, multinuclear NMR spectroscopy, and a single-crystal X-ray diffraction study.