Das Prasenjit, Chattaraj Pratim Kumar
Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.
Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India.
J Phys Chem A. 2020 Nov 25;124(47):9801-9810. doi: 10.1021/acs.jpca.0c08306. Epub 2020 Nov 15.
calculations have been performed for a series of binuclear sandwich complexes, M(η-L). It has been observed that the eclipsed and staggered conformations have almost equal amount of energies. The M-M bond lengths are comparable with those in the free M molecules (M = Be, Mg). The nuclear-independent chemical shift (NICS) values indicate the aromaticity of these complexes. The stability of Be(η-L) complexes is higher than that of the Mg(η-L) complexes. The natural bond orbital (NBO) analysis and electron density descriptors proved the existence of a single covalent M-M bond in an M fragment. It has been observed that each M-M bond contains a non-nuclear attractor (NNA) at the center of the respective bond. The Laplacian of electron density [∇ρ()] is negative at the NNAs. The energy decomposition analysis (EDA) showed that M and 2L represent the bonding interaction in the complexes. All of the designed binuclear sandwich complexes behave as electrides.
已对一系列双核夹心配合物M(η-L)进行了计算。据观察，重叠构象和交错构象的能量几乎相等。M-M键长与游离M分子（M = Be、Mg）中的键长相当。核独立化学位移（NICS）值表明了这些配合物的芳香性。Be(η-L)配合物的稳定性高于Mg(η-L)配合物。自然键轨道（NBO）分析和电子密度描述符证明了M片段中存在单个共价M-M键。据观察，每个M-M键在各自键的中心都包含一个非核吸引子（NNA）。电子密度的拉普拉斯算子[∇ρ()]在NNA处为负。能量分解分析（EDA）表明，M和2L代表了配合物中的键合相互作用。所有设计的双核夹心配合物都表现为电子化物。
