Highly Fluxional [Y(C(SiH(CH3)2)3)3]: A DFT Characterization of Structure and NMR Spectra

被引：1

作者：

Lein, Matthias ^{[1
,2
]}

Harrison, John A. ^{[3
]}

机构：

[1] Victoria Univ Wellington, Sch Chem & Phys Sci, Wellington 6140, New Zealand

[2] Massey Univ Auckland, New Zealand Inst Adv Study, Ctr Theoret Chem & Phys, Auckland 0745, New Zealand

[3] Massey Univ Auckland, Inst Nat Sci, Auckland 0745, New Zealand

来源：

JOURNAL OF CHEMICAL THEORY AND COMPUTATION | 2011年 / 7卷 / 02期

关键词：

AGOSTIC INTERACTIONS; MOLYBDENUM COMPLEXES; CHEMISTRY; ALKYL;

D O I：

10.1021/ct100663y

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The structure and NMR spectroscopic properties of [Y(C(SiH(CH3)(2))(3))(3)] are investigated with density functional theory calculations. The existence of a C-3 principal axis that was found experimentally is reproduced, but the calculations also find that the symmetry of the equilibrium structure of [Y(C(SiH(CH3)(2))(3))(3)] has to be reduced from the experimentally suggested C-3v or C-3h to C-3 in order to explain the observed SiH NMR chemical shifts. We show that the apparent mirror plane relating two agostic SiH(CH3)(2) groups on each ligand is caused by the rapid interchange of the position of the third ligand, which could only be observed at much lower temperatures than used previously in the experiments.

引用

页码：385 / 389

页数：5

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