Mandal Dipendu, Man Wing Y, Rosair Georgina M, Welch Alan J
Institute of Chemical Sciences, School of Engineering & Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, Scotland.
Acta Crystallogr C Struct Chem. 2015 Sep;71(Pt 9):793-8. doi: 10.1107/S2053229615014539. Epub 2015 Aug 15.
Both rac-[1-(1'-4'-Cp-4',1',12'-closo-CoC2B10H11)-4-Cp-4,1,12-closo-CoC2B10H11]·2THF (Cp is cyclopentadienyl and THF is tetrahydrofuran) or [Co2(C5H5)2(C4H22B20)]·2C4H8O, (1), and meso-[1-(1'-4'-Cp-4',1',12'-closo-CoC2B10H11)-4-Cp-4,1,12-closo-CoC2B10H11] or [Co2(C5H5)2(C4H22B20)], (2), were prepared by thermolysis of a rac/meso mixture of the precursor species [1-(1'-4'-Cp-4',1',6'-closo-CoC2B10H11)-4-Cp-4,1,6-closo-CoC2B10H11] and were separated, spectroscopically characterized and studied crystallographically. Cage C-atom identification was accomplished by both the vertex-to-centroid distance and boron-hydrogen distance methods, and, in both cases, the structure established crystallographically is fully consistent with the spectroscopic data. Both the rac-(1) and meso-(2) forms share the same overall conformation (Co-C-C'-Co' ca 136°) and show clear evidence of intramolecular steric crowding resulting in tilted cyclopentadienyl ligands.
rac-[1-(1'-4'-环戊二烯基-4',1',12'-闭式-钴代-二碳硼烷-10-十一氢)-4-环戊二烯基-4,1,12-闭式-钴代-二碳硼烷-10-十一氢]·2四氢呋喃(环戊二烯基为Cp,四氢呋喃为THF)或[Co₂(C₅H₅)₂(C₄H₂₂B₂₀)]·2C₄H₈O,(1),以及内消旋-[1-(1'-4'-环戊二烯基-4',1',12'-闭式-钴代-二碳硼烷-10-十一氢)-4-环戊二烯基-4,1,12-闭式-钴代-二碳硼烷-10-十一氢]或[Co₂(C₅H₅)₂(C₄H₂₂B₂₀)],(2),通过前驱体物种[1-(1'-4'-环戊二烯基-4',1',6'-闭式-钴代-二碳硼烷-10-十一氢)-4-环戊二烯基-4,1,6-闭式-钴代-二碳硼烷-10-十一氢]的外消旋/内消旋混合物的热解制备,进行了分离、光谱表征和晶体学研究。笼状碳原子的识别通过顶点到质心距离法和硼氢距离法完成,并且在两种情况下,晶体学确定的结构与光谱数据完全一致。外消旋-(1)和内消旋-(2)形式都具有相同的整体构象(Co-C-C'-Co'约136°),并显示出分子内空间拥挤导致环戊二烯基配体倾斜的明显证据。