Structural distortions of coordinated ketene molecule induced by the pseudo Jahn-Teller effect
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GORINCHOY, Natalia. Structural distortions of coordinated ketene molecule induced by the pseudo Jahn-Teller effect. In: Chemistry Journal of Moldova, 2016, nr. 2(11), pp. 99-104. ISSN 1857-1727. DOI: https://doi.org/10.19261/cjm.2016.11(2).09
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Chemistry Journal of Moldova
Numărul 2(11) / 2016 / ISSN 1857-1727 /ISSNe 2345-1688

Structural distortions of coordinated ketene molecule induced by the pseudo Jahn-Teller effect
DOI: https://doi.org/10.19261/cjm.2016.11(2).09
CZU: 54

Pag. 99-104

Gorinchoy Natalia
 
Institute of Chemistry of the Academy of Sciences of Moldova
 
Proiecte:
 
Disponibil în IBN: 26 decembrie 2016


Rezumat

It is demonstrated that the only reason of structural distortions of ketene molecule coordinated in the complexes VCp2-H2C2O (I) and Pt(PPh3)2-H2C2O (II) is the pseudo Jahn-Teller effect (PJTE) induced by the orbital charge transfers (OCTs) by coordination. It is shown that the η2-(C-O) coordination and the in-plane b2-type distortion of ketene in the complex (I) is due to the PJTE induced by the back donation to its LUMO 3b2 (πCO*). The η2-(C-C) coordination mode, as well as the out-of-plane b1-type distortion of the molecule in the complex (II) is caused by two OSTs: from the HOMO 2b1(πCC) to the metal, and from the dxy- atomic orbital (AO) of the atom of Pt to the vacant 3b1(πCC*) molecular orbital (MO) of ketene, thus being the result of the diorbital Pt-ketene interaction. The necessary parameters of the PJTE were estimated by considering the excited states of free ketene molecule, and the values of the OSTs were obtained from the electronic structure calculations of the complexes.

Cuvinte-cheie
pseudo Jahn-Teller effect,

orbital charge transfers, ketene excited states, metal ketene complex