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异金属镍/镉复合固体中卤素依赖性多样性和弱相互作用：结构与理论研究

Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation.

作者信息

Nesterova Oksana V, Petrusenko Svitlana R, Skelton Brian W, Nesterov Dmytro S

机构信息

Centro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.

Department of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Str., 01601 Kyiv, Ukraine.

出版信息

Molecules. 2023 Nov 18;28(22):7652. doi: 10.3390/molecules28227652.

DOI:10.3390/molecules28227652
PMID:38005374
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10674445/
Abstract

Three novel heterometallic Ni/Cd coordination compounds [Ni(en)][CdCl]∙3dmso (), [Ni(en)(dmf)][CdBr] (), and [Ni(en)]CdI () have been synthesized through the self-assembly process in a one-pot reaction of cadmium oxide, nickel salt (or nickel powder), NHX (X = Cl, Br, I), and ethylenediamine in non-aqueous solvents dmso (for ) or dmf (for and ). Formation of the one- () or three-dimensional ( and ) hydrogen-bonded frameworks has been observed depending on the nature of the [CdX] counter-anion, as well as on the nature of the solvent. The electronic structures of [Ni(en)] and [Ni(en)(dmf)] cations were studied at the DFT and CASSCF levels, including the ab initio ligand field theory (AILFT) calculations. The non-covalent intermolecular contacts between the cationic nickel and anionic cadmium blocks in the solid state were investigated by the QTAIM analysis. The mechanism of ligand substitution at the nickel center in [Ni(en)(dmf)] was theoretically investigated at the ωB97X-D4/ma-def2-TZVP//DLPNO-CCSD(T)/ma-def2-TZVPP level. The results demonstrate that thermodynamic factors are structure-determining ones due to low energy barriers of the rotation of dmf ligands in [Ni(en)(dmf)] (below 3 kcal mol) and the reversible transformation of [Ni(en)(dmf)] into [Ni(en)] (below 20 kcal mol).

摘要

通过氧化镉、镍盐（或镍粉）、NH₄X（X = Cl、Br、I）和乙二胺在非水溶剂二甲基亚砜（用于化合物1）或二甲基甲酰胺（用于化合物2和3）中的一锅法自组装过程，合成了三种新型异金属镍/镉配位化合物[Ni(en)₂][CdCl₄]∙3dmso（化合物1）、[Ni(en)₂(dmf)₂][CdBr₄]（化合物2）和[Ni(en)₂]CdI₄（化合物3）。根据[CdX₄]抗衡阴离子的性质以及溶剂的性质，观察到了一维（化合物1）或三维（化合物2和3）氢键框架的形成。在DFT和CASSCF水平上研究了[Ni(en)₂]²⁺和[Ni(en)₂(dmf)₂]²⁺阳离子的电子结构，包括从头算配体场理论（AILFT）计算。通过QTAIM分析研究了固态中阳离子镍和阴离子镉块之间的非共价分子间相互作用。在ωB97X-D4/ma-def2-TZVP//DLPNO-CCSD(T)/ma-def2-TZVPP水平上对[Ni(en)₂(dmf)₂]²⁺中镍中心的配体取代机理进行了理论研究。结果表明，由于[Ni(en)₂(dmf)₂]²⁺中dmf配体旋转的能垒较低（低于3 kcal mol⁻¹）以及[Ni(en)₂(dmf)₂]²⁺向[Ni(en)₂]²⁺的可逆转变（低于20 kcal mol⁻¹），热力学因素是决定结构的因素。

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