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

• Published in: Coordination chemistry reviews Vol. 238; pp. 55 - 82
• Main Authors: Frenking, Gernot, Wichmann, Karin, Fröhlich, Nikolaus, Loschen, Christoph, Lein, Matthias, Frunzke, Jan, Rayón, Vı́ctor M
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.03.2003
• Subjects: Bonding analysis; Donoracceptor bonds; Energy partitioning; Main group complexes; Transition metal complexes; ETS, extended transition state; Main group complexes; ZORA, zero order regular approximation; LUMO, lowest unoccupied molecular orbital; Energy partitioning; Transition metal complexes; Donoracceptor bonds; ADF, Amsterdam density functionals; TZ2P, triple zeta plus 2 polarization; HOMO, higher occupied molecular orbital; HF, Hartree-Fock; TM, transition metal; EDA, energy decomposition analysis; VSEPR, valence shell electron pair repulsion; MO, molecular orbital; Bonding analysis; HSAB, hard and soft acids and bases; TZP, triple zeta plus polarization; VB, valence bond
• ISSN: 0010-8545; 1873-3840
• DOI: 10.1016/S0010-8545(02)00285-0

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) 5TMPX 3 (TM=Cr, Mo, W; X=H, Me, F, Cl); (d) main group complexes with phosphane ligands X 3BPY 3 and X 3Al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).