TY - JOUR
T1 - Theoretical studies on all-metal binuclear sandwich-like complexes M 2(η4-E4)2 (M=Al, Ga, In; E=Sb, Bi)
AU - Wang, Congzhi
AU - Zhang, Xiuhui
AU - Lu, Jian
AU - Li, Qianshu
PY - 2012/8
Y1 - 2012/8
N2 - A series of all-metal binuclear sandwich-like complexes with the formula M2(η4-E4)2 (M=Al, Ga, In; E=Sb, Bi) was studied by density functional theory (DFT). The most stable conformer for each of the M2(η4-E4)2 species is the staggered one with D4d symmetry. The centred metal-metal bond in each M2(η4-E4) 2 species is a covalent single bond, with the main contributors to these covalent bonds being the a1 and e orbitals. For all these species, the interactions between the centred metal atoms and the allmetal ligands are covalent; η4-Sb42- has a stronger ability to stabilize metal-metal bonds than η4-Bi4 2-. Nucleusindependent chemical shifts (NICS) values and molecular orbital (MO) analysis reveal that the all-metal η-Sb4 2- and η4-Bi42- ligands in M2(η-E4)2 possess conflicting aromaticity (o- antiaromaticity and π aromaticity), which differs from the all-metal multiple aromatic unit Al42-. In addition, all of these M2(η4-E4)2 species are stable according to the dissociation energies of M2(η 4-E4)2 →2 M(η4-E 4) and M2(η4-E4)2 → 2 M+2E4, and these stable species can be synthesized by two-step substitution reactions: CpZnZnCp + 2E42- →[E4ZnZnE4]2- +2Cp- and [E 4ZnZnE4]2- + 2 M2+ →E4MME4+2Zn+.
AB - A series of all-metal binuclear sandwich-like complexes with the formula M2(η4-E4)2 (M=Al, Ga, In; E=Sb, Bi) was studied by density functional theory (DFT). The most stable conformer for each of the M2(η4-E4)2 species is the staggered one with D4d symmetry. The centred metal-metal bond in each M2(η4-E4) 2 species is a covalent single bond, with the main contributors to these covalent bonds being the a1 and e orbitals. For all these species, the interactions between the centred metal atoms and the allmetal ligands are covalent; η4-Sb42- has a stronger ability to stabilize metal-metal bonds than η4-Bi4 2-. Nucleusindependent chemical shifts (NICS) values and molecular orbital (MO) analysis reveal that the all-metal η-Sb4 2- and η4-Bi42- ligands in M2(η-E4)2 possess conflicting aromaticity (o- antiaromaticity and π aromaticity), which differs from the all-metal multiple aromatic unit Al42-. In addition, all of these M2(η4-E4)2 species are stable according to the dissociation energies of M2(η 4-E4)2 →2 M(η4-E 4) and M2(η4-E4)2 → 2 M+2E4, and these stable species can be synthesized by two-step substitution reactions: CpZnZnCp + 2E42- →[E4ZnZnE4]2- +2Cp- and [E 4ZnZnE4]2- + 2 M2+ →E4MME4+2Zn+.
KW - All-metal
KW - Binuclear sandwich-like
KW - Conflicting aromaticity
KW - Density functional theory
UR - https://www.scopus.com/pages/publications/84864719849
U2 - 10.1007/s00894-012-1362-y
DO - 10.1007/s00894-012-1362-y
M3 - Article
C2 - 22350296
AN - SCOPUS:84864719849
SN - 1610-2940
VL - 18
SP - 3577
EP - 3586
JO - Journal of Molecular Modeling
JF - Journal of Molecular Modeling
IS - 8
ER -