Are J(Si-H) NMR coupling constants really a probe for the existence of nonclassical H-Si interactions?
Are J(Si-H) NMR coupling constants really a probe for the existence of nonclassical H-Si interactions?
复制标题
J(Si-H) NMR 耦合常数真的是非经典 H-Si 相互作用存在的探针吗？
DOI：
--
复制
发表时间：
2003
影响因子：
15
通讯作者：
G. Nikonov
中科院分区：
文献类型：
--
作者：
Stuart R. Dubberley;S. Ignatov;N. Rees;A. G. Razuvaev;P. Mountford;G. Nikonov
合成了一系列钽的双甲硅烷基配合物Cp（ArN）Ta（PMe 3）（H）（SiClnR 3-n）（n = 0-3），并通过~（29）Si NMR、X射线衍射和密度泛函理论计算进行了研究。观察到氢化物和甲硅烷基配体之间的J（Si-H）耦合常数从14 Hz（n = 0）到50 Hz（n = 3）的前所未有的增加，然而，根据DFT计算，这并不对应于硅和氢化物配体之间更强的成键相互作用，其中最强的相互作用是n = 1。
A series of hydridosilyl complexes of tantalum, Cp(ArN)Ta(PMe3)(H)(SiClnR3-n) (n = 0-3), was prepared and studied by 29Si NMR, X-ray diffraction, and DFT calculations. An unprecedented increase of the J(Si-H) coupling constant between the hydride and silyl ligands from 14 Hz for n = 0 to 50 Hz n = 3 was observed, which however, according to DFT calculations, does not correspond to stronger bonding interaction between silicon and hydride ligands, with the strongest interaction being for n = 1.