TY - JOUR
T1 - Towards a rigorously defined quantum chemical analysis of the chemical bond in donor-acceptor complexes
AU - Frenking, Gernot
AU - Wichmann, Karin
AU - Fröhlich, Nikolaus
AU - Loschen, Christoph
AU - Lein, Matthias
AU - Frunzke, Jan
AU - Rayón, Víctor M.
PY - 2003/3
Y1 - 2003/3
N2 - 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-T1); (c) transition metal complexes with phosphane ligands (CO) 5 TMPX 3 (TM = Cr, Mo, W; X = H, Me, F, Cl); (d) main group complexes with phosphane ligands X 3 B-PY 3 and X 3 Al-PY 3 (X = H, F, Cl; Y = F, Cl, Me, CN); (e) transition metal metallocene complexes Fe(η 5 -E 5 ) 2 and FeCp(η 5 -E 5 ) (E = CH, N, P, As, Sb); (f) main group metallocenes ECp 2 (E = Be-Ba, Zn, Si-Pb) and ECp (E = Li-Cs, B-Tl).
AB - 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-T1); (c) transition metal complexes with phosphane ligands (CO) 5 TMPX 3 (TM = Cr, Mo, W; X = H, Me, F, Cl); (d) main group complexes with phosphane ligands X 3 B-PY 3 and X 3 Al-PY 3 (X = H, F, Cl; Y = F, Cl, Me, CN); (e) transition metal metallocene complexes Fe(η 5 -E 5 ) 2 and FeCp(η 5 -E 5 ) (E = CH, N, P, As, Sb); (f) main group metallocenes ECp 2 (E = Be-Ba, Zn, Si-Pb) and ECp (E = Li-Cs, B-Tl).
KW - Bonding analysis
KW - Donor-acceptor bonds
KW - Energy partitioning
KW - Main group complexes
KW - Transition metal complexes
UR - http://www.scopus.com/inward/record.url?scp=0037509929&partnerID=8YFLogxK
U2 - 10.1016/S0010-8545(02)00285-0
DO - 10.1016/S0010-8545(02)00285-0
M3 - 文章
AN - SCOPUS:0037509929
SN - 0010-8545
VL - 238-239
SP - 55
EP - 82
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
ER -