| Autor: |
Murillo J; Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, USA. asfortier@utep.edu., Bhowmick R; Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, USA. Bess.Vlaisavljevich@usd.edu., Harriman KLM; Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada., Gomez-Torres A; Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, USA. asfortier@utep.edu., Wright J; Department of Physics, Illinois Institute of Technology, Chicago, IL, 60616, USA., Miró P; Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, USA. Bess.Vlaisavljevich@usd.edu., Metta-Magaña A; Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, USA. asfortier@utep.edu., Murugesu M; Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada., Vlaisavljevich B; Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, USA. Bess.Vlaisavljevich@usd.edu., Fortier S; Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, USA. asfortier@utep.edu. |
| Abstrakt: |
An unprecedented sandwich complex of the actinides is synthesized from the treatment of [UI 2 (HMPA) 4 ]I (HMPA = OP(NMe 2 ) 3 ) (2) with 3 equiv. of K(C 14 H 10 ) to give the neutral, bis(arenide) species U(η 6 -C 14 H 10 )(η 4 -C 14 H 10 )(HMPA) 2 (1). Solid-state X-ray, SQUID magnetometry, and XANES analyses are consistent with tetravalent uranium supported by [C 14 H 10 ] 2- ligands. In one case, treatment of 1 with an equiv. of AgOTf led to the isolation of U(η 6 -C 14 H 10 ) 2 (HMPA)(THF) (3), formed from ring migration and haptotropic rearrangement. Complete active space (CASSCF) calculations indicate the U-C bonding to solely consist of π-interactions, presenting a unique electronic structure distinct from classic actinide sandwich compounds. |
