Menacer Rafik, May Abdelghani, Belkhiri Lotfi, Mousser Abdelhamid
Laboratoire de Physicochimie Analytique et Cristallochimie des Matériaux Organométalliques et Biomoléculaires LPACMOB, Département de Chimie, Université Frères Mentouri, 25017, Constantine, Algeria.
Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques CRAPC, BP 384, Zone Industrielle, Bou-ismail, Tipaza, RP 42004, Algeria.
J Mol Model. 2017 Nov 28;23(12):358. doi: 10.1007/s00894-017-3523-5.
The nature of the chemical metal-metal bond in M(CO) (M = Mn, Re, Tc) dinuclear decacarbonyls complexes was investigated for the first time using the natural orbital chemical valence (NOCV) approach combined with the extended transition state (ETS) for energy decomposition analysis (EDA). The optimized geometries carried out at different levels of theory BP86, BLYP, BLYPD and BP86D, showed that the latter method, i.e., BP86D, led to the best agreement with X-ray experimental measurements. The BP86D/TZP results revealed that the computed covalent contribution to the metal-metal bond are 60.5%, 54.1% and 52.0% for Mn-Mn, Re-Re and Tc-Tc, respectively. The computed total interaction energies resulting from attractive terms (ΔE and ΔE ), correspond well to experimental predictions, based on bond lengths and energy interaction analysis for the studied complexes.
首次使用自然轨道化学价（NOCV）方法并结合扩展过渡态（ETS）进行能量分解分析（EDA），研究了M(CO)（M = Mn、Re、Tc）双核十羰基配合物中化学金属-金属键的性质。在不同理论水平BP86、BLYP、BLYPD和BP86D下进行的优化几何结构表明，后一种方法即BP86D与X射线实验测量结果的吻合度最佳。BP86D/TZP结果表明，对于Mn-Mn、Re-Re和Tc-Tc，计算得出的金属-金属键的共价贡献分别为60.5%、54.1%和52.0%。基于对所研究配合物的键长和能量相互作用分析，由吸引项（ΔE 和ΔE ）得出的计算总相互作用能与实验预测结果吻合良好。
