Syntheses and structures of sterically congested linear and branched cobalta[n]triangulanes.
Syntheses and structures of sterically congested linear and branched cobalta[n]triangulanes.
复制标题
空间拥挤的线性和支链钴[n]三角烷的合成和结构。
作者：
S. Kozhushkov;J. Foerstner;A. Kakoschke;D. Stellfeldt;Li Yong;R. Wartchow;A. de Meijere;H. Butenschön
用亚甲基环丙烷(3)或双环丙叉(4)以及用它们的螺环丙烷化类似物亚甲基螺戊烷(7)、亚环丙螺戊烷(10)或处理{eta(5):eta(1)[2-(二叔丁基膦基-P)乙基]环戊二烯基}氯化钴(I)(5) 7,7'-双(二螺[2.0.2.1]亚庚基) (15) 在钠汞齐存在下，在 -50 摄氏度下，分别提供了稳定的钴络合物 6、9、8、11 和 16，分离产率分别为 72%、83%、84%、86% 和 54%。配合物14和16也可通过乙烯配合物{eta(5):eta(1)[2-(二叔丁基膦基-P)乙基]环戊二烯基}(eta(2)-乙烯)钴(I)(12)与13和15的配体交换获得，产率分别为79%和52%。配合物9、14和16的X射线晶体结构分析以及所有配合物的NMR光谱数据表明它们可以被视为线性和支化的钴[n]三角烷。通过差热分析-热重分析 (DTA-TG) 分析确定配合物 6、8 和 9 在 109、145 和 160 摄氏度的热稳定性。
Treatment of {eta(5):eta(1)[2-(di-tert-butylphosphanyl-P)ethyl]cyclopentadienyl}cobalt(I) chloride (5) with methylenecyclopropane (3) or bicyclopropylidene (4), as well as with their spirocyclopropanated analogues methylenespiropentane (7), cyclopropylidenespiropentane (10), or 7,7'-bi(dispiro[2.0.2.1]heptylidene) (15) in the presence of sodium amalgam at -50 degrees C, furnished the stable cobalt complexes 6, 9, 8, 11, and 16, respectively, in 72, 83, 84, 86, and 54 % isolated yield, respectively. The complexes 14 and 16 were also obtained by ligand exchange of the ethene complex {eta(5):eta(1)[2-(di-tert-butylphosphanyl-P)ethyl]cyclopentadienyl}(eta(2)-ethene)cobalt(I) (12) with 13 and 15 in 79 and 52 % yield, respectively. The X-ray crystal-structure analyses of complexes 9, 14, and 16, as well as the NMR-spectroscopic data of all complexes, reveal that they can be regarded as linear and branched cobalta[n]triangulanes. The thermal stability of complexes 6, 8, and 9 up to 109, 145, and 160 degrees C was determined by differential thermal analysis-thermogravimetry (DTA-TG) analysis.