Effects of density functionals and dispersion interactions on geometries, bond energies and harmonic frequencies of EUX3 (E=N, P, CH; X=H, F, Cl)

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2014

“…The calculated frequencies with BLYP functional closely resembled with experimental values. The bond dissociation energies of the U≡P bonds were found to be significantly smaller than the U≡N and U≡CH bonds [136]. The synthesis of the mono(imidazolin-2-iminato) actinide(IV) complexes (Im R N)An[N(SiMe 3 ) 2 ] 3 was accomplished by the protonolysis reaction between the respective imidazolin-2-imine (Im R NH, R = t Bu, Mes, Dipp; Dipp = 2,6-diisopropylphenyl) and the readily availableactinide metallacycles [(Me 3 Si)N] 2 An[κ 2 C,N-CH 2 SiMe 2 N(SiMe 3 )] (Scheme 132; An = U, Th).…”

“…of TEMPO to form 1-(2-propen-1-yloxy)-2,2,6,6-tetramethylpiperidine (allyl-TEMPO) and Cp * 2 Th(η 1 -C 3 H 5 )(η 1 -TEMPO) (Scheme 159). [155] M a n u s c r i p t M a n u s c r i p t 136 In contrast, Cp * 2 ThBr 2 reacted with 2 equiv. of TEMPO by loss of C 5 Me 5 to form dimeric (C 5 Me 5 ) 2 and (η 2 -TEMPO) 2 ThBr 2 , in which the TEMPO -anions bind through oxygen and nitrogen.…”

Interplay between London Dispersion, Hubbard U, and Metastable States for Uranium Compounds

“…However, the large atomic size of the actinides should result in large C 6 dispersion coefficients, and previous work has shown that dispersion interactions can significantly affect the volume of ionic solids, such as the alkali halides . Few publications have studied the effect of including a dispersion correction on predicted properties of gas-phase actinide complexes, − and none, to the authors’ knowledge, have considered solid-state actinide compounds.…”