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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)
+ Show Author Affiliations

Abstract The coordination of t BuNC and CO with the diarsenido complexes (C 5 Me 5 ) 2 An( η 2 ‐As 2 Mes 2 ), An=Th, U, has been investigated. For the first time, a comparison between isostructural complexes of Th IV and U IV 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 Th IV and U IV 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 An IV 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 Univ. of New York (SUNY), Albany, NY (United States); Univ. of Missouri, Columbia, MO (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE
Grant/Contract Number:
SC0001136; SC0021273
OSTI ID:
1976298
Alternate ID(s):
OSTI ID: 1821240
Journal Information:
Chemistry - A European Journal, Vol. 27, Issue 58; ISSN 0947-6539
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Linked Research (2)

Figures / Tables (5)

Scheme 1(p. 2)figure Scheme 1
Figure 1(p. 3)figure Figure 1
Table 1(p. 3)table Table 1
Table 2(p. 3)table Table 2
Figure 2(p. 4)figure Figure 2

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