Multiple fluxional processes in chiral (pentaphenylcyclopentadienyl)iron complexes: X-ray crystal structure of (C5Ph5)Fe(CO)(PMe3)(HC:O) and the barriers to aryl, phosphine, and tripodal rotation in (C5Ph5)Fe(CO)(PMe2Ph)C(O)Et
Multiple fluxional processes in chiral (pentaphenylcyclopentadienyl)iron complexes: X-ray crystal structure of (C5Ph5)Fe(CO)(PMe3)(HC:O) and the barriers to aryl, phosphine, and tripodal rotation in (C5Ph5)Fe(CO)(PMe2Ph)C(O)Et
复制标题
手性(五苯基环戊二烯基)铁配合物中的多重通量过程：(C5Ph5)Fe(CO)(PMe3)(HC:O)的X射线晶体结构以及(C5Ph5)Fe(CO)中芳基、膦和三足旋转的势垒
DOI：
10.1021/om00014a046
复制
发表时间：
1994
期刊：
影响因子：
2.8
通讯作者：
C. Lapinte
中科院分区：
文献类型：
--
作者：
Lijuan Li;A. Decken;B. Sayer;M. McGlinchey;Patrick Bregaint;J. Thépot;L. Toupet;J. Hamon;C. Lapinte
12.868（7）A，c= 25.861（9）A，λ = 93.95（5），V= 8021（1）A3，Z= 8。空间拥挤分子（C_5Ph_5）Fe（C_0）（PPhMe_2）C（0）Et的~（13）C和~（31）P变温核磁共振谱表明存在两个流动过程。当手性三脚架的旋转在NMR时间尺度上变慢时，双环碳的5倍简并性被分裂。此外，外围苯环或膦配体的减慢旋转可产生非对映异构体的混合物。这两个过程的能垒分别为8.7±0.3和11.7±0.3 kcal mol ~（-1），表明这两种流动行为是不相关的。
12.868 (7) A, c= 25.861 (9) A, ß= 93.95 (5), V= 8021 (1) A3, and Z= 8. 13C and 31P variabletemperature NMR spectra of the sterically crowded molecule (C5Ph5) Fe (C0)(PPhMe2) C (0) Et reveal the presence of two fluxional processes. When rotation of the chiral tripod becomes slow on the NMR time scale, the 5-fold degeneracy of the cyclopentadienyl ring carbons is split. Moreover, slowed rotation of either the peripheral phenyl rings or the phosphine ligand can give rise to a mixture of diastereomers. The barriersfor these two processes (8.7±0.3 and 11.7±0.3 kcal mol-1, respectively) demonstrate that the two types of fluxional behavior are not correlated.