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
Mahnoosh Hakimi-Tabar, Mohammad Vakili, Vahidreza Darugar, Mahmood Akbari, Sayyed Faramarz Tayyari, Mohammad Reza Housaindokht
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引用次数: 0
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.
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.