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

R.N. Galimullin^*, A.V. Plotnikova^**, E.V. Kolpakova^***,  A.I. Kuramshin

Kazan Federal University, Kazan, 420008 Russia

E-mail: ^*ramis-fenix@mail.ru, ^**anezka_93@mail.ru, ^***argironet@gmail.com

Received December 9, 2019

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DOI: 10.26907/2542-064X.2020.1.17-32

For citation: Galimullin R.N., Plotnikova A.V., Kolpakova E.V., Kuramshin A.I. Mono- and bisphenanthroline complexes of chromium group metals with conjugated heterodienes – a theore­tical and experimental study. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2020, vol. 162, no. 1, pp. 17–32. doi: 10.26907/2542-064X.2020.1.17-32. (In Russian)

Abstract

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.

Keywords: 1,10-phenanthroline, chromium group complexes, heterodienes, quantum chemical calculations

Acknowledgments. The study was supported by the Russian Foundation for Basic Research (project no. 18-33-00445).

Figure Captions

Fig. 1. Energy diagram of the interaction of hexacarbonylmolybdenum(0) with phenanthroline.

Fig. 2. Energy diagram of the interaction of hexacarbonylchrome(0) with phenanthroline.

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