Towards a rigorously defined quantum chemical analysis of the chemical bond in donor-acceptor complexes

被引：388

作者：

Frenking, G ^{[1
]}

Wichmann, K ^{[1
]}

Fröhlich, N ^{[1
]}

Loschen, C ^{[1
]}

Lein, M ^{[1
]}

Frunzke, J ^{[1
]}

Rayón, VM ^{[1
]}

机构：

[1] Univ Marburg, Fachbereich Chem, D-35042 Marburg, Germany

来源：

COORDINATION CHEMISTRY REVIEWS | 2003年 / 238卷

关键词：

bondina analysis; donor-acceptor bonds; energy partitioning; transition metal complexes; main group complexes;

D O I：

10.1016/S0010-8545(02)00285-0

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The results of an energy decomposition analysis of various classes of donor-acceptor complexes of transition metals and main-group elements are discussed. It is shown that the nature of the chemical bond can be quantitatively identified in terms of Pauli repulsion. electrostatic attraction and covalent bonding. The covalent and electrostatic contributions to the interatomic attraction can be precisely given by using a well defined partitioning method in conjunction with accurate quantum chemical calculations of the geometries and bond energies. This is shown for six classes of donor-acceptor complexes: (a) transition metal carbonyl complexes; (b) transition metal complexes with Group-13 diyl ligands ER (E B-Tl); (c) transition metal complexes with phosphane ligands (CO)(5)TMPX3 (TM Cr, Mo, W; X = H, Me, F, Cl); (d) main group complexes with phosphane ligands X3B-PY3 and X3Al-PY3 (X = K F Cl; Y F, Cl, Me, CN); (e) transition metal metallocene complexes Fe(eta(5)-E-5)(2) and FeCp(eta(5) -E-5) (E = CH. N, P, As, Sb); (f) main group metallocenes ECp2 (E = Be-Ba, Zn, Si-Pb) and ECp (E = Li-Cs, B-Tl). (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：55 / 82

页数：28

共 114 条

[111] CASSCF CALCULATION ON DIOXYGEN HEME COMPLEX WITH EXTENDED BASIS SET [J].