Oxidation states, atomic charges and orbital populations in transition metal complexes

被引:67
作者
Aullon, Gabriel [1 ]
Alvarez, Santiago [1 ]
机构
[1] Univ Barcelona, Dept Quim Inorgan, IQTC, Barcelona, Spain
关键词
Transition metals; Oxidation states; Population analysis; DFT calculations; Pauling electroneutrality rule; GAUSSIAN-BASIS SETS; PSEUDOPOTENTIALS; D(8); LI;
D O I
10.1007/s00214-009-0537-9
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
The differences and similarities between calculated atomic charge and formal oxidation state in transition metal complexes are discussed in the light of density functional theory calculations on a variety of four-coordinate complexes. It is shown that the oxidation state formalism provides a framework for the classification of families of compounds related by ligand substitution or redox processes, and can neither be replaced by nor deduced from net atomic charges.
引用
收藏
页码:67 / 73
页数:7
相关论文
共 29 条
[1]   Shape maps and polyhedral interconversion paths in transition metal chemistry [J].
Alvarez, S ;
Alemany, P ;
Casanova, D ;
Cirera, J ;
Llunell, M ;
Avnir, D .
COORDINATION CHEMISTRY REVIEWS, 2005, 249 (17-18) :1693-1708
[2]  
ALVAREZ S, 2008, UNPUB
[3]  
[Anonymous], 1960, The Nature of the Chemical Bond, 3rd ed
[4]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[5]   Choice of coordination number in d10 complexes of group 11 metals [J].
Carvajal, MA ;
Novoa, JJ ;
Alvarez, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (05) :1465-1477
[6]   A NEW POPULATION ANALYSIS BASED ON ATOMIC POLAR TENSORS [J].
CIOSLOWSKI, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (22) :8333-8336
[7]   Stereochemistry and spin state in four-coordinate transition metal compounds [J].
Cirera, Jordi ;
Ruiz, Eliseo ;
Alvarez, Santiago .
INORGANIC CHEMISTRY, 2008, 47 (07) :2871-2889
[8]   Synthesis and properties of donor-free bis(difluoromethyl)cadmium, (CF2H)(2)Cd - NMR spectroscopic detection and structure of tetrakis(difluoromethyl)cuprate(III) and related compounds [J].
Eujen, R ;
Hoge, B ;
Brauer, DJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 519 (1-2) :7-20
[9]   Structural characterization of representative d(7), d(8), and d(9) transition metal complexes of bis(o-carborane) [J].
Harwell, DE ;
McMillan, J ;
Knobler, CB ;
Hawthorne, MF .
INORGANIC CHEMISTRY, 1997, 36 (25) :5951-5955
[10]   A Piece of the Picture-Misunderstanding of Chemical Concepts [J].
Jansen, Martin ;
Wedig, Ulrich .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (52) :10026-10029