Investigation of the dithiolene ligand conformation in analogous U(IV)/U(V) complexes:: X-ray diffraction and density functional theory analysis of the U•••(C=C) interaction

被引:19
作者
Belkhiri, Lotfi
Arliguie, Therese
Thuery, Pierre
Fourmigue, Marc
Boucekkine, Abdou
Ephritikhine, Michel
机构
[1] Univ Mentouri Constantine, Fac Sci, Dept Chim, Lab Chim Mol Controle Environm & Mesures Phys Chi, Constantine 25017, Algeria
[2] CEA Saclay, CNRS, URA 331, DSM,DRECAM,Serv Chim Mol, F-91191 Gif Sur Yvette, France
[3] Univ Rennes 1, CNRS, UMR 6226, F-35042 Rennes, France
关键词
D O I
10.1021/om060083d
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Elucidation of the crystal structure of the dianionic complex [Na(18-crown-6)(thf)(2)](2)[U(COT)(dddt)(2)] (COT = eta(8)-C8H8, dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate), complementing that of [Na(18-crown-6)( thf)][U(COT)(dddt)(2)], allowed the first structural comparison of analogous uranium( IV) and -( V) compounds with anionic sulfur ligands. The distinct conformations of the dithiolene ligands, exo-exo and exo-endo in the uranium (IV) and -(V) complexes, respectively, are the observable manifestation of the differences in the metal-ligand bonding according to the oxidation state of the metal. The relationship between electronic structure, bonding, and conformational changes in these dianionic uranium(IV) and anionic uranium(V) species and the hypothetical neutral uranium(VI) counterpart has been investigated in the framework of relativistic density functional theory. The calculations reveal the occurrence in the uranium(V) anionic species of a significant intramolecular interaction involving the 5f metal orbitals and the C=C double bond of the endo dithiolene ligand, which stabilizes its peculiar exo-endo conformation. Such an interaction does not exist in the uranium(IV) complex.
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页码:2782 / 2795
页数:14
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