The β-Agostic Structure in (C5Me5)2Sc(CH2CH3): Solid-State NMR Studies of (C5Me5)2Sc-R (R=Me, Ph, Et)

被引：22

作者：

Culver, Damien B. ^{[1
]}

Huynh, Winn ^{[1
]}

Tafazolian, Hosein ^{[1
]}

Ong, Ta-Chung ^{[2
]}

Conley, Matthew P. ^{[1
]}

机构：

[1] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA

[2] Univ Calif Los Angeles, Dept Chem, Los Angeles, CA 90095 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 30期

基金：

美国国家科学基金会;

关键词：

agostic interactions; cyclopentadienyl ligands; NMR spectroscopy; sandwich complexes; scandium; DENSITY-FUNCTIONAL THEORY; CHEMICAL-SHIFT; QUADRUPOLAR NUCLEI; METATHESIS CATALYSTS; ALKYL COMPLEXES; MAGIC-ANGLE; TENSORS; SPECTROSCOPY; POLYMERIZATION; METALLOCENE;

D O I：

10.1002/anie.201805738

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Multinuclear solid-state NMR studies of Cp*Sc-2-R (Cp*=pentamethylcyclopentadienyl; R=Me, Ph, Et) and DFT calculations show that the Sc-Et complex contains a beta-CH agostic interaction. The static central transition Sc-45 NMR spectra show that the quadrupolar coupling constants (C-q) follow the trend of Ph approximate to Me>Et, indicating that the Sc-R bond is different in Cp*Sc-2-Et compared to the methyl and phenyl complexes. Analysis of the chemical shift tensor (CST) shows that the deshielding experienced by C beta in Sc-CH2CH3 is related to coupling between the filled sigma(C-C) orbital and the vacant pi*(SC...HC) orbital.

引用

页码：9520 / 9523

页数：4

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