Comparative study of the lanthanide (Ln) and actinide (An) triflate complexes M(OTf).

Theoretical studies on the lanthanide and actinide triflate complexes M(OTf) 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) 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) and the ideal one is U(OTf). The highest population contribution of 5 d orbital compared to 5 f orbital in Th-O bond of Th(OTf) explains the distortion. The intramolecular rearrangement of the OTf ligands in Ln(OTf) generates two conformers. In Yb(OTf), the pseudo-eclipsed and the staggered conformations are stable and can be isolated. [ABSTRACT FROM AUTHOR]