Oxidation states "naturally": A Natural Bond Orbital method for determining transition metal oxidation states

被引：15

作者：

Webster, Albert J. ^{[1
]}

Mueller, Chelsea M. ^{[1
,3
]}

Foegen, Neil P. ^{[1
]}

Sit, Patrick H. -L. ^{[2
]}

Speetzen, Erin D. ^{[1
]}

Cunningham, Drew W. ^{[1
,4
]}

D'Acchioli, Jason S. ^{[1
]}

机构：

[1] Univ Wisconsin, Dept Chem, Stevens Point, WI 54481 USA

[2] City Univ Hong Kong, Sch Energy & Environm, Hong Kong, Hong Kong, Peoples R China

[3] Northwestern Univ, Dept Chem, 2145 Sheridan Rd, Evanston, IL 60208 USA

[4] Univ Calif Irvine, Dept Chem, 1102 Nat Sci 2, Irvine, CA 92697 USA

来源：

POLYHEDRON | 2016年 / 114卷

基金：

美国国家科学基金会;

关键词：

Oxidation states; Density functional theory; Natural Bond Orbital (NBO) theory; Dewar-Chatt-Duncanson model; Transition metals; CAMBRIDGE STRUCTURAL DATABASE; EFFECTIVE CORE POTENTIALS; ELECTRONIC-STRUCTURE; MOLECULAR CALCULATIONS; CRYSTAL-STRUCTURE; X-RAY; TEMPERATURE; SALTS; COMPLEXES; QUANDARY;

D O I：

10.1016/j.poly.2015.11.018

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The oxidation state (OS) concept is arguably one of the most useful formalisms in chemistry. OSs are used to explain a variety of phenomena at transition metal centers, from chemical reactivity to spectroscopic properties. Attempting to define a theoretical method of evaluating this construct, however, has resulted in a broad debate among chemists, particularly inorganic chemists. With this in mind we propose a simple method for determining the oxidation states of transition metal centers using Natural Bond Orbital (NBO) theory. A description of the wavefunction (or electron density in the case of density functional theory, as presented in this investigation) is obtained from quantum chemical calculations. The 5 x 5 d-orbital Natural Atomic Orbital (NAO) occupation matrix is then obtained, and diagonalized. The resulting eigenvalues deliver the d-orbital occupations, fkom which the oxidation states can be inferred. The NBO-driven method also allowed us to probe "ambiguous" cases where a strong pi-acid is involved in bonding (in our case, CO). The scope of the method is described, along with promising future applications. (C) 2015 Elsevier Ltd. All rights reserved.

引用

页码：128 / 132

页数：5

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