Title: Backbonding in Thorium(IV) and Uranium(IV) Diarsenido Complexes with tBuNC and CO

Journal Article · · Chemistry - A European Journal
 [1];  [2];  [1];  [1];  [2];  [1]
  1. University of Missouri, Columbia, MO (United States)
  2. State University of New York (SUNY), Buffalo, NY (United States)
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The coordination of tBuNC and CO with the diarsenido complexes (C5Me5)2An(η2-As2Mes2), 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.

Research Organization:
State University of New York (SUNY), Albany, NY (United States); University of Missouri, Columbia, MO (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001136; SC0021273
OSTI ID:
1976298
Journal Information:
Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 58 Vol. 27; ISSN 0947-6539
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinide
backbonding
carbonyl
isocyanide
synthesis