Backbonding in Thorium(IV) and Uranium(IV) Diarsenido Complexes with tBuNC and CO.
Chemistry
; 27(58): 14396-14400, 2021 Oct 19.
Article
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| MEDLINE
| ID: mdl-34404114
ABSTRACT
The coordination of tBuNC and CO with the diarsenido complexes (C5 Me5 )2 An(η2 -As2 Mes2 ), An=Th, U, has been investigated. For the first time, a comparison between isostructural complexes of ThIV and UIV has been possible with CO; density functional calculations indicated an appreciable amount of π backbonding that originates from charge transfer from an actinide-arsenic sigma bond. The calculated CO stretching frequencies in the ThIV and UIV diarsenido complexes are consistent with the experimental measurements, both show large shifts to lower frequency. We demonstrate that the π backbonding is crucial to explaining the red shifts of CO frequency upon AnIV complex formation. Interestingly, this interaction essentially correlates to the parallel orientation of π*(C-O) orbitals relative to the An-As bond.
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Bases de datos:
MEDLINE
Idioma:
En
Revista:
Chemistry
Asunto de la revista:
QUIMICA
Año:
2021
Tipo del documento:
Article
País de afiliación:
Estados Unidos