Bis(arene) actinide sandwich complexes, ({eta}{sup 6}-C{sub 6}H{sub 3}R{sub 3}){sub 2}An: Linear or bent?

Journal Article · Wed Nov 03 04:00:00 EST 1999 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja9923991· OSTI ID:20013684

Li, J; Bursten, B E

The syntheses of the sandwich complexes ferrocene, ({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}-Fe, in 1951 and uranocene, ({eta}{sup 8}-C{sub 8}H{sub 8}){sub 2}U, in 1968 ushered in the modern eras of organotransition metal and organoactinide chemistry, respectively. Ferrocene and uranocene are examples of linear sandwich complexes, that is, those in which the (ring centroid)-M-(ring centroid) angle (denoted {theta}) is 180{degree}. In the case of ({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}M chemistry, a number of bent ({theta} < 180{degree}) complexes are known when M is a main-group or rare-earth element. The explanation for the bent structures of these complexes has been the subject of some debate concerning the relative importance of covalent, electrostatic, and steric interactions. The authors report optimized geometries of Bz{sub 2}An (An = Th-Am) and ({eta}{sup 6}-C{sub 6}H{sub 3}R{sub 3}){sub 2}An (An = Th, U, Pu; R = Me, {sup t}Bu) obtained by using local density approximation (LDA) and Perdew-Wang (PW91) gradient-corrected relativistic density functional theory (DFT) methods. These DFT methods are found to be able to reproduce the experimental geometries and vibrational frequencies of organoactinide complexes with satisfactory accuracy. The (TTB){sub 2}An calculations that are reported here are, to date, the largest full geometry optimizations to be carried out on an actinide system.

• Research Organization: Ohio State Univ., Columbus, OH (US)
• Sponsoring Organization: US Department of Energy
• DOE Contract Number: FG02-86ER13529
• OSTI ID: 20013684
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 43 Vol. 121; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
FERROCENE
MOLECULAR STRUCTURE
PLUTONIUM COMPLEXES
SYNTHESIS
THORIUM COMPLEXES
URANIUM COMPLEXES