f-Orbital to carbonyl 2. pi. back-bonding: the electronic structures of (eta/sup 5/-C/sub 5/H/sub 5/)/sub 3/UCO and (eta/sup 5/-C/sub 5/H/sub 5/)/sub 3/UOC

Journal Article · Wed Oct 28 04:00:00 EST 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00256a007· OSTI ID:5521912

Bursten, B E; Strittmatter, R J

The electronic structures of Cp/sub 3/UCO (1), (Cp/sub 3/UCO)/sup +/ (1/sup +/), and Cp/sub 3/UOC (2) have been investigated by X..cap alpha..-SW molecular orbital calculations with quasirelativistic corrections. Two major interactions of 1 are discussed. The CO 5sigma lone pair interacts primarily with the empty U 6d orbitals to form the U-CO sigma bond, and extensive U 5f ..-->.. CO 2..pi.. back-bonding is observed. In 1/sup +/, the sigma interaction is not affected by oxidation while the ..pi.. back-bonding interaction is decreased. In contrast to 1,2 shows no ..pi.. back-bonding interaction, and the CO 4sigma orbital interacts with the filled U 6p orbitals. Upon the basis of these calculations, it is believed that 2 would be unstable relative to 1.

• Research Organization: Ohio State Univ., Columbus
• DOE Contract Number: FG02-86ER13529
• OSTI ID: 5521912
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:22; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPOUNDS
CARBONYLS
CHEMICAL BONDS
DATA
ELECTRONIC STRUCTURE
INFORMATION
MOLECULAR ORBITAL METHOD
NUMERICAL DATA
THEORETICAL DATA
URANIUM COMPOUNDS