Structure and bonding in NbX5 X = (F, Cl, Br and I) complexes: a molecular orbital perspective in the C-H bond activation

被引：8

作者：

Silva, Telles Cardoso ^{[1
]}

Pires, Maira dos Santos ^{[1
]}

de Castro, Alexandre Alves ^{[1
]}

Tavares Lacerda, Livia Clara ^{[1
]}

Juliaci Rocha, Marcus Vinicius ^{[2
]}

Ramalho, Teodorico Castro ^{[1
,3
]}

机构：

[1] Univ Fed Lavras, Dept Chem, Univ Campus, BR-37200000 Lavras, MG, Brazil

[2] Fluminense Fed Univ, Inst Chem, Dept Phys Chem, BR-24020141 Niteroi, RJ, Brazil

[3] Univ Hradec Kralove, Fac Informat & Management, Ctr Basic & Appl Res, Hradec Kralove, Czech Republic

来源：

THEORETICAL CHEMISTRY ACCOUNTS | 2018年 / 137卷 / 11期

关键词：

Niobium pentahalide complexes; Energy decomposition analysis (EDA); QTAIM; C-H bond activation; Ligands effects; COORDINATION-COMPLEXES; TANTALUM PENTAHALIDES; METHANE; NIOBIUM; REACTIVITY; CONVERSION; ENERGIES; LIGANDS; SURFACE; ATOM;

D O I：

10.1007/s00214-018-2348-3

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

In the present work, theoretical studies of the reactivity and stability of the NbX5 complexes (X = F, Cl, Br and I) were carried out in the methane C-H bond activation. To study the chemical bonds formation of these complexes, an energy decomposition analysis was performed together with QTAIM calculations. The main results indicated that the interaction and binding energies are higher for NbF5 in relation to the halogen series. The niobium complexes gaps are influenced by the electron-egativity of the halogens and the Nb-X bonding lengths. According to the energy diagram, the electrons less connected to the bond are sigma Nb-I; on the other hand, the best electron acceptor is sigma*Nb-F. The QTAIM calculations confirmed stronger Nb-X chemical bonds in NbF5 complexes. Regarding the reactivity of the niobium complexes, the overall results indicate better thermodynamic and kinetic conditions for the NbF5 complex.

引用

页数：13

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