Understanding the nature of the bonding in transition metal complexes: from Dewar's molecular orbital model to an energy partitioning analysis of the metal-ligand bond

被引:153
作者
Frenking, G [1 ]
机构
[1] Univ Marburg, Fachbereich Chem, D-35039 Marburg, Germany
关键词
DFT; molecular orbital calculations; synergic bonding; carbonyls; group; 13-diyl;
D O I
10.1016/S0022-328X(01)01154-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The results of an energy partitioning analysis of three classes of transition metal complexes are discussed. They are (i) neutral and charged isoelectronic hexacarbonyls TM(CO)(6)(q) (TMq = Hf2-, Ta-, W, Re+, Os2+, Ir3+); (ii) Group-13 diyl complexes (CO)(4)Fe-ER (E = B, Al, Ga, In, Tl; R = Cp, Ph), Fe(ECH3)(5) and Ni(ECH3)(4); (iii) complexes with cyclic pi -donor ligands Fe(Cp)(2) and Fe(eta (5) -N-5)(2). The results show that Dewar's molecular orbital model can be recovered and that the orbital interactions can become quantitatively expressed by accurate quantum chemical calculations. However, the energy analysis goes beyond the MO model and gives a much deeper insight into the nature of the metal-ligand bonding. It addresses also the question of ionic versus covalent bonding as well as the relative importance of sigma and pi bonding contributions. (C) 2001 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:9 / 23
页数:15
相关论文
共 90 条
[11]  
2-Z
[12]  
Braunschweig H., 1998, ANGEW CHEM, V110, P3355
[13]  
Braunschweig H., 1998, Angew. Chem., V110, P1882
[14]   REGULAR 2-COMPONENT PAULI-LIKE EFFECTIVE-HAMILTONIANS IN DIRAC THEORY [J].
CHANG, C ;
PELISSIER, M ;
DURAND, P .
PHYSICA SCRIPTA, 1986, 34 (05) :394-404
[15]   OLEFIN CO-ORDINATION COMPOUNDS .3. INFRA-RED SPECTRA AND STRUCTURE - ATTEMPTED PREPARATION OF ACETYLENE COMPLEXES [J].
CHATT, J ;
DUNCANSON, LA .
JOURNAL OF THE CHEMICAL SOCIETY, 1953, (OCT) :2939-2947
[16]   Theory predicts that the weaker π-accepting ligand diaminoborylene occupies the equatorial position in (OC)4Fe-B(NH2):: theoretical study of (OC)4Fe-B(NH2) and (OC)4Fe-BH [J].
Chen, Y ;
Frenking, G .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2001, (04) :434-440
[17]  
Cotton F., 1999, ADV INORGANIC CHEM
[18]   Remarks on the gallium to iron bond in an Ar*GaFe(CO)4 molecule [J].
Cotton, FA ;
Feng, XJ .
ORGANOMETALLICS, 1998, 17 (02) :128-130
[19]   Synthesis and characterization of a terminal borylene (boranediyl) complex [J].
Cowley, AH ;
Lomelí, V ;
Voigt, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (25) :6401-6402
[20]   Ligand effects in transition metal dihydrogen complexes: A theoretical study [J].
Dapprich, S ;
Frenking, G .
ORGANOMETALLICS, 1996, 15 (21) :4547-4551