COMPARATIVE STUDY OF THE LANTHANIDE (Ln) AND ACTINIDE (An) TRIFLATE COMPLEXES M(OTf)n
M. Lemmouchi1, D. Hannachi1,2, N. Ouddai1
1Universite El-Hadj Lakhdar, Batna, Algeria
2University Farhat Abbasse, Setif, Algeria
Keywords: triflate, lanthanide, actinide, coordination, intramolecular rearrangement
Abstract
Theoretical studies on the lanthanide and actinide triflate complexes M(OTf) n where M = La, Ce, Gd, Yb, Lu, Th, U, Np, Pu, Am, Cm, Bk, and No; n = 3 and 4, are carried out using functional density theory (DFT). The study of An(OTf)3 complexes showed that the three OTf groups are bidentate, generating a trigonal prism (TP). Two limiting structures of TP are observed; the most distorted is the thorium triflate Th(OTf)3 and the ideal one is U(OTf)3. The highest population contribution of 5 d orbital compared to 5 f orbital in Th-O bond of Th(OTf)3 explains the distortion. The intramolecular rearrangement of the OTf ligands in Ln(OTf)3 generates two conformers. In Yb(OTf)3, the pseudo-eclipsed and the staggered conformations are stable and can be isolated.
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