Theoretical studies of the electronic properties and reactions of organoactinide complexes using density functional theory

NUCL 18

P. Jeffrey Hay, pjhay@lanl.gov, Ping Yang, pyang@lanl.gov, Enrique R. Batista, erb@lanl.gov, and Richard L. Martin, rlmartin@lanl.gov. Theoretical Division, Los Alamos National Laboratory, MS B268, Los Alamos, NM 87545
The structures, electronic properties and excited states of organoactinide complexes are explored with the aid of DFT calculations. Complexes of Th and U involving the ketimide ligand (C5Me5)2An[N=C(Ph)(R)]2 exhibit unusual spectroscopic and electrochemical properties and enhanced metal-ligand bond orders. Theoretical calculations have guided the interpretation of spectroscopic and electrochemical results and have also provided a description of the role of 6d and 5f orbitals in the bonding. In another area, activation of sp2 and sp3 C-H bonds in 2-methyl-pyridine by (C5Me5)2An(Me)2 complexes has been explored by calculating the transition states and products for these distinct reaction pathways. From the results one can explain the differences in the observed chemistries between the Th and U complexes. Additional topics include 5f-5f interactions in bimetallic assemblies and unusual bonding in organometallic U(VI) analogues of the uranyl species.
 

Computational Actinide and Transactinide Chemistry: Progress and Perspectives
8:10 AM-12:00 PM, Sunday, August 19, 2007 Boston Park Plaza -- Franklin Rm, Oral

Division of Nuclear Chemistry & Technology

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007