Assessment of density functional methods for the study of vanadium and rhenium complexes with thiolato ligands.

VANADIO

RENIO

BIBLIOGRAFIA NACIONAL QUIMICA

2010

Herein, we report the assessment of six DFT methods (BP86, TPSS, B3LYP, X3LYP, PBE1PBE, BH&HLYP) in describing the nature of the chemical bonds, structural, and electronic properties of the closed-shell oxocomplex of Re(V) [ReO(bdt)2] and the open-shell oxocomplex of V(IV) [VO(bdt)2]2 (bdt2 = 1,2-benzenedithiolato). Several basis sets were employed, and different effective core potentials were taken as variables into account. PBE1PBE is found to be the best overall performer in describing M@S bonds. It is followed by two groups composed in turn of BP86, TPSS, and BH&HLYP, and another one including B3LYP and X3LYP. For the M@O bonds, the performance has a direct dependency on the Hartree–Fock exchange. On going from the pure GGA (BP86) and m-GGA (TPSS) to BH&HLYP, a sensible improvement is obtained for the Re@O bond distances. However, for the V@O bond the opposite is true, being BH&HLYP the worst choice. The M@S and M@O chemical bonds have been analyzed in terms of the natural bond orbital theory. All sulfur atoms participate in r bonds strongly polarized toward the non-metal, in which the hybridization at the metal has mainly d character and at the non-metal, p character. For the Re@O bonds, interesting features were found. This work shows that PBE1PBE in combination with the MIDI! basis set and the Stuttgart energy consistent pseudopotentials for metals is the best methodology for the study of rhenium and vanadium complexes with thiolato ligands. We have tested our hypothesis performing comparative calculations for the [Re6S8X6]4 (X = Cl, Br, I) hexanuclear clusters. The results obtained at the PBE1PBE/STMIDI significantly improve those published previously and the computational cost is small. Therefore, we recommend this methodology to study large of transition metal complexes containing thiolato ligands.

Journal of Molecular Structure : THEOCHEM v. 941, no. 1-3, 2010. -- p. 1-9

Elsevier

2010

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doi:10.1016/j.theochem.2009.10.020

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