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单体、低配位的第 12 族配合物中的构象异构现象,由萘基取代的间三联苯配体稳定。

Conformational isomerism in monomeric, low-coordinate group 12 complexes stabilized by a naphthyl-substituted m-terphenyl ligand.

机构信息

School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.

出版信息

Chemistry. 2013 Aug 19;19(34):11446-53. doi: 10.1002/chem.201301872. Epub 2013 Jul 12.

Abstract

The synthesis and characterization of the first series of low-coordinate bis(terphenyl) complexes of the Group 12 metals, [Zn(2,6-Naph2 C6 H3 )2 ] (1), [Cd(OEt2 )(2,6-Naph2 C6 H3 )2 ] (2) and [Hg(OEt2 )(2,6-Naph2 C6 H3 )2 ] (3) (Naph=1-C10 H7 ) are described. The naphthyl substituents of the terphenyl ligands confer considerable steric bulk, and as a result of limited flexibility introduce multiple conformations to these unusual systems. In the solid state, complex 1 features a two-coordinate Zn centre with the ligands oriented in a syn/anti conformation, whereas the three-coordinate distorted T-shaped complexes 2 and 3 feature the ligands in the syn/syn configurations. The results of DFT calculations are in good agreement with the solid-state configurations for these complexes and support the spectroscopic measurements, which indicate several conformers in solution.

摘要

我们合成并表征了第一系列的 Group 12 金属的低配位双(三联苯)配合物,[Zn(2,6-Naph2 C6 H3 )2 ](1),[Cd(OEt2 )(2,6-Naph2 C6 H3 )2 ](2)和[Hg(OEt2 )(2,6-Naph2 C6 H3 )2 ](3)(Naph=1-C10 H7 )。三联苯配体的萘基取代基赋予了相当大的空间位阻,并且由于其有限的灵活性,为这些不寻常的体系引入了多种构象。在固态下,配合物 1 具有一个二配位的 Zn 中心,配体呈顺/反构象取向,而三配位的扭曲 T 型配合物 2 和 3 则具有顺/顺构型的配体。DFT 计算的结果与这些配合物的固态构型非常吻合,并支持了光谱测量结果,表明在溶液中有几种构象。

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