Mono- And bisphenanthroline complexes of chromium group metals with conjugated heterodienes – A theoretical and experimental study

© 2020 Kazan Federal University. All rights reserved. A theoretical study was carried out (with the help of the density functional method, based on LANL2DZ and the modified BHandHLYP functional) for the energy, electronic, and geometric properties of (heterodien)M(phen)(CO)2 and (heterodien)M(phen)2 complexes. The obtained results indicate the possibility of using phenanthroline ligand to stabilize heterodiene structures. A number of previously undescribed carbonylphenanthroline, bis-phenanthroline carbonyl, oxodien- and thioxodienfenanthroline (and bis-phenanthroline oxodien/thioxodien) coordination compounds were synthesized. A low lability of the phenolanthroline-stabilized organometallic compound was demonstrated by the NMR studies. The prospects of applying phenanthroline as a “ligand standard” to synthesize organometallic compounds of VI-group metals were confirmed. Dimethylphosphite was added via a multiple C=O bond of the oxodiene and dienone complexes of the chromium group metals

Mono- and bisphenanthroline complexes of chromium group metals with conjugated heterodienes – a theoretical and experimental study

A theoretical study was carried out (with the help of the density functional method, based on LANL2DZ and the modified BHandHLYP functional) for the energy, electronic, and geometric properties of (heterodien)M(phen)(CO)2 and (heterodien)M(phen)2 complexes. The obtained results indicate the possibility of using phenanthroline ligand to stabilize heterodiene structures. A number of previously undescribed carbonylphenanthroline, bis-phenanthroline carbonyl, oxodien- and thioxodienfenanthroline (and bis-phenanthroline oxodien/thioxodien) coordination compounds were synthesized. A low lability of the phenolanthroline-stabilized organometallic compound was demonstrated by the NMR studies. The prospects of applying phenanthroline as a “ligand standard” to synthesize organometallic compounds of VI-group metals were confirmed. Dimethylphosphite was added via a multiple C=O bond of the oxodiene and dienone complexes of the chromium group metals

Selection of Appropriate Quantum-Chemical Model for Calculations of Properties of Chromium Group Complexes via DFT

The selection of a pair of functional/basis for the most adequate quantum-chemical determination of the geometric and electronic properties of chromium group metal complexes with polydent heterocyclic ligands has been carried out. When selecting a suitable model, such parameters as allowable accuracy and acceptable time of calculation have been taken into account. It has been found that the accuracy of calculations depends on the number of basis functions in-volved in the calculation model – the error tends to decrease with the increase in their number. The ac-curacy of calculations also increases with introduction of the polarized orbitals 2d2p and 3df3pd in the quantum-chemical model and the diffuse orbitals p, pp, ppp in the basis, respectively. The results obtained by using non-hybrid functionals with large basis functions are comparable to the calculations performed in less time with the help of hybrid functionals. The optimal ratio for the accuracy of calculation results compared to the time for study of the coordi-nation compounds can be achieved by using the PBE0 hybrid functional and TZVPP basis functions