Towards Hexagonal Planar Nickel: A Dispersion-Stabilised Tri-Lithium Nickelate

被引：13

作者：

Borys, Andryj M. ^{[1
]}

Malaspina, Lorraine A. ^{[1
]}

Grabowsky, Simon ^{[1
]}

Hevia, Eva ^{[1
]}

机构：

[1] Univ Bern, Dept Chem Biochem & Pharm, Freiestr 3, CH-3012 Bern, Switzerland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 39期

基金：

瑞士国家科学基金会;

关键词：

Complementary Bonding Analysis; London Dispersion; Nickel; Organolithium; Transition-Metal Complexes; LONDON DISPERSION; COMPLEXES; ATOMS;

D O I：

10.1002/anie.202209797

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Advancing the understanding of lithum nickelate complexes, here we report a family of homoleptic organonickelate complexes obtained by reacting Ni(COD)(2) and lithium aryl-acetylides in the presence of the bidentate donor TMEDA. These compounds represent rare examples of low-valent transition-metals supported solely by organolithium ligands. Whilst the solid-state structures indicate a hexagonal planar geometry around Ni-0 with Ni-Li bonds, bonding analysis via QTAIM, NCI, NBO and ELI methods reveals that the Ni-Li interactions are repulsive in nature, characterising these complexes as tri-coordinated. London dispersion forces between TMEDA and the organic substituents on nickel are found to play a crucial role in the stabilisation and thus isolation of these complexes. Preliminary reactivity studies demonstrate that the homoleptic lithium nickelates undergo stoichiometric cross-coupling with PhI to give dinickel clusters containing both anionic acetylide and neutral alkyne ligands.

引用

页数：6

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