Comparisons between yttrium and titanium N-heterocyclic carbene complexes in the search for early transition metal NHC backbonding interactions

被引：32

作者：

Arnold, Polly L. ^{[1
]}

Zlatogorsky, Sergey ^{[1
]}

Jones, Natalie A. ^{[1
]}

Carmichael, Christopher D. ^{[1
]}

Liddle, Stephen T. ^{[2
]}

Blake, Alexander J. ^{[2
]}

Wilson, Claire ^{[3
]}

机构：

[1] Univ Edinburgh, Sch Chem, Edinburgh EH9 3JJ, Midlothian, Scotland

[2] Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England

[3] Rigaku Europe, Sevenoaks, Kent, England

来源：

INORGANIC CHEMISTRY | 2008年 / 47卷 / 19期

基金：

英国工程与自然科学研究理事会;

关键词：

D O I：

10.1021/ic801046u

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The d(0) yttrium N-heterocyclic carbene compound YL3 (L = OCMe2CH2[C{N(CHCH)NPr}]) has been made and structurally characterized. It adopts a mer configuration of the three bidentate ligands. A comparison of this with the isostructural d(1) titanium complex TiL3 is Made in order to seek experimental evidence of a pi-bonding contribution to the M-C bond. This has been augmented by DFT calculations. Experimentally, the metal radius-corrected Ti-C distance is shorter than the Y-C distance, suggesting a T-bonding contribution in the d(1) complex, but the computational data suggest that a shorter or bond might simply be formed by the more strongly polarizing titanium cation. From the potassium reduction of TiL(OPr')(3), only a byproduct arising from silicone grease activation was isolable, identified as a mixed-valent, multinuclear, d(0)/d(1) cluster [(TiL2)-L-III{Pr'OSiMe2O}K2OTiIV(OPr')(4)](2) in which the carbene ligands are bound to the Ti-III centers in preference to Ti-IV, with longer Ti-C distances than those found in TiL3.

引用

页码：9042 / 9049

页数：8

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