School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Chemistry. 2013 Aug 19;19(34):11446-53. doi: 10.1002/chem.201301872. Epub 2013 Jul 12.
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.
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。
