Charge transfer effects on the paramagnetic properties of the [M(C₈H₈)₂] and M(C₅H₅)(C₈H₈); M = Ti, Zr, Hf and Th, complexes

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• 作者：Dayá ; n Pá ; ez-Herná ; ndez ; ^{d.paezhernandez@yahoo.es} ; Ramiro Arratia-Pé ; rez ; ^{rarratia@unab.cl}
• 关键词：EPR ; g Tensor ; ZORA ; Spin&ndash ; orbit
• 刊名：Polyhedron
• 出版年：2012
• 期刊代码：87_02775387
• 类别：ch
• 出版时间：4 April, 2012
• 卷：36
• 期：1
• 页码：69-72
• 文件大小：300 K

摘要

A systematic study of a series of (19e) [M(COT)₂]ⁿ, (n = 鈭? for Th and n = +1 for Ti, Zr, Hf) and (17e) MCpCOT, where Cp and COT represent cyclopentadienyl [C₅H₅]^{鈭?/sup> and cyclooctatetraene [C₈H₈]鈭?, respectively, has been performed using relativistic density functional theory with the two components ZORA Hamiltonian for the inclusion of scalar and spin-orbit effects. The EPR parameters were obtained as second order properties employing the EPR/NMR algorithms with an inclusion of spin-orbit coupling. The obtained g tensor values are in good agreement with the experimental results and the calculations reveals that each ground state in all systems are nonbonding and of mostly of character. There is a low spin density at protons site resulting from a direct delocalization of the unpaired electron spin on the 1s orbitals.}