An Intramolecularly Base-Stabilized Diphosphagermylene and Two Unusual Germanium(II) Ate Complexes: A Structural, NMR, and DFT Study
作者:Keith Izod、William McFarlane、Ben Allen、William Clegg、Ross W. Harrington
DOI:10.1021/om0501125
日期:2005.4.1
treatment of GeI2 or GeCl2·dioxane with 3 equiv of 5 yields the cage ate complex R(C6H4-2-CH2NMe2)P}3GeK (9). The solid-state structures of 7−9 have been determined by X-ray crystallography, and the dynamic behavior of 6−9 in solution has been studied by multielement and variable-temperature NMR experiments. DFT calculations on the model complex (Me)(C6H4-2-CH2NMe2)P}GeCl (6a) indicate that inversion at germanium
GeCl 2 ·二恶烷与1当量的R(C 6 H 4 -2-CH 2 NMe 2)P} K(5)之间的反应产生杂配物R(C 6 H 4 -2-CH 2 NMe 2)P} GeCl(6)[R =(Me 3 Si)2 CH]。用2当量的钾盐5处理GeI 2可获得分子内稳定的均化的,分子内碱稳定的二磷亚age基R(C 6 H 4 -2-CH 2 NMe 2)P} 2 Ge(7),产量高。相反,用乙醚中的2当量的R(C 6 H 4 -2-CH 2 NMe 2)P} Li(4)处理GeI 2可再现地产生异常的络合物R(C 6 H 4 -2- CH 2 NMe 2)P} 2 GeLi 2 I 2(OEt 2)3(8),而用3当量5处理GeI 2或GeCl 2 ·二恶烷则产生笼状络合物R(C 6 H 4 -2) -CH 2NMe 2)P} 3 GeK(9)。的固态结构7 - 9已经通过X射线晶体学确定,并且动态行为6