The effect of alkyl substituents in the β-side on the conformation, molecular structure, and copper-oxygen bond strength of bis(β-diketonato)copper(II) complexes by DFT results and experimental vibrational and UV spectra

IF 1.6 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Transition Metal Chemistry Pub Date : 2023-07-22 DOI:10.1007/s11243-023-00545-8

Mahnoosh Hakimi-Tabar, Mohammad Vakili, Vahidreza Darugar, Mahmood Akbari, Sayyed Faramarz Tayyari, Mohammad Reza Housaindokht

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Abstract

The conformation, geometry, and relative energies of bis (2,6-dimethylheptane-3,5-dionato)copper(II), (Cu(DIMHD)₂), and bis (5,5-dimethylhexane-2,4-dionato)copper(II), Cu(DMHD)₂ have been assayed through using calculated results from atoms-in-molecules (AIM) analysis, time-dependent density functional theory (TD-DFT), natural bond orbital (NBO), and density functional theory (DFT). The electronic and vibrational spectra of these compounds have also been studied using experimental infrared, Raman, and ultraviolet (UV) spectra. All theoretical and empirical vibrational frequencies of the mentioned compounds have been assigned. The DFT was used to characterize the conformers of the complexes mentioned above, as well as the observed vibrational and UV spectra. Similar complexes, including copper (II) acetylacetonate Cu(AA)₂, bis(3,5-heptanedionato)copper(II) (Cu(HPD)₂), and copper (II) 2,2,6,6-tetramethylheptane-3,5-dionate (Cu(TMHD)₂), have been chosen to evaluate the influence of isopropyl (iPr) and tert-Butyl (t-Bu) groups substituents instead of methyl and ethyl groups. All experimental, spectroscopic, and DFT results confirmed that the O-Cu bond strength in Cu(DIMHD)₂ and Cu(DMHD)₂ is between Cu(TMHD)₂ and Cu(AA)₂ and close to Cu(HPD)₂.

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通过 DFT 结果和实验振动光谱与紫外光谱研究β-侧烷基取代基对双（β-二酮）铜（II）配合物的构象、分子结构和铜氧键强度的影响

利用原子分子分析（AIM）、时间相关密度泛函理论（TD-DFT）、天然键轨道（NBO）和密度泛函理论（DFT）的计算结果，对双（2,6-二甲基庚烷-3,5-二酮酸）铜（II）（Cu(DIMHD)2）和双（5,5-二甲基己烷-2,4-二酮酸）铜（II）（Cu(DMHD)2）的构象、几何和相对能量进行了分析。此外，还利用实验红外光谱、拉曼光谱和紫外光谱研究了这些化合物的电子和振动光谱。上述化合物的所有理论和经验振动频率均已确定。DFT 被用来描述上述配合物的构象以及观察到的振动光谱和紫外光谱。还选择了类似的配合物，包括乙酰丙酮铜 (II)、双(3,5-庚二酮酸)铜 (Cu(HPD)2) 和 2,2,6,6-四甲基庚烷-3,5-二酮酸铜 (Cu(TMHD)2)，以评估取代甲基和乙基的异丙基 (iPr) 和叔丁基 (t-Bu) 的影响。所有实验、光谱和 DFT 结果都证实，Cu(DIMHD)2 和 Cu(DMHD)2 中的 O-Cu 键强度介于 Cu(TMHD)2 和 Cu(AA)2 之间，接近 Cu(HPD)2。

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来源期刊

Transition Metal Chemistry 化学-无机化学与核化学

CiteScore

3.60

自引率

0.00%

发文量

审稿时长

1.3 months

期刊介绍： Transition Metal Chemistry is an international journal designed to deal with all aspects of the subject embodied in the title: the preparation of transition metal-based molecular compounds of all kinds (including complexes of the Group 12 elements), their structural, physical, kinetic, catalytic and biological properties, their use in chemical synthesis as well as their application in the widest context, their role in naturally occurring systems etc. Manuscripts submitted to the journal should be of broad appeal to the readership and for this reason, papers which are confined to more specialised studies such as the measurement of solution phase equilibria or thermal decomposition studies, or papers which include extensive material on f-block elements, or papers dealing with non-molecular materials, will not normally be considered for publication. Work describing new ligands or coordination geometries must provide sufficient evidence for the confident assignment of structural formulae; this will usually take the form of one or more X-ray crystal structures.