The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes

A.I. Kuramshin*, E.V. Kolpakova**, R.A. Cherkasov***, V.I. Galkin****

Kazan Federal University, Kazan, 420008 Russia

E-mail: *fea_naro@mail.ru, **argironet@gmail.com, ***Rafael.Cherkasov@kpfu.ru, ****Vladimir.Galkin@kpfu.ru

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Abstract

Using quantum-chemical calculations carried out for interpretation of the experimentally discovered reactivity of 1-hetero-1,3-dienes that are mono- and bidentally coordinated with the transition metal core, we have revealed that the difference in hydrophosphorylation directions of the free organic molecule and the same molecule involved in the coordination sphere of the transition metal can be explained by either weakening or complete loss of conjugation between the C=C and C=X fragments as a result of coordination.

In the case of monodentate coordination of heterodiene with the transition metal according to the η2(C,C)-type, the conjugation weakening is suggested to be maximum for the transition metal characterized by the minimum electronegativity, which predetermines the increased contribution of the metalcyclopropane resonance structure into the general bonding mode. Organometallic compounds having the heterodiene ligand bidentally coordinated demonstrate the conjugation weakening parallel to the metal radius.

Keywords: quantum-chemical calculations, metal-organic derivatives of chromium group metals, density functional (DFT), conjugation, stress energy

Figure captions

Fig. 1. Dependence of the energy of heterodiene ligand stress via the metal core on the electronegativity of the metal.

Fig. 2. Dependence of the energy of heterodiene ligand stress via the metal core on the valent radius of the metal.

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For citation: Kuramshin A.I., Kolpakova E.V., Cherkasov R.A., Galkin V.I. The conjugation stress of ligand via metal core as the cause of changes in the reactivity of coordinated 1-hetero-1,3-dienes. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2016, vol. 158, no. 2, pp. 176–186. (In Russian)

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