Theoretical studies on all-metal binuclear sandwich-like complexes M2(η 4-E 4) 2 (M=Al, Ga, In; E=Sb, Bi)

J Mol Model. 2012 Aug;18(8):3577-86. doi: 10.1007/s00894-012-1362-y. Epub 2012 Feb 16.

Abstract

A series of all-metal binuclear sandwich-like complexes with the formula M(2)(η(4)-E(4))(2) (M=Al, Ga, In; E=Sb, Bi) was studied by density functional theory (DFT). The most stable conformer for each of the M(2)(η(4)-E(4))(2) species is the staggered one with D (4d) symmetry. The centred metal-metal bond in each M(2)(η(4)-E(4))(2) species is a covalent single bond, with the main contributors to these covalent bonds being the a(1) and e orbitals. For all these species, the interactions between the centred metal atoms and the all-metal ligands are covalent; η(4)-Sb (4) (2-) has a stronger ability to stabilize metal-metal bonds than η(4)-Bi (4) (2-). Nucleus-independent chemical shifts (NICS) values and molecular orbital (MO) analysis reveal that the all-metal η(4)-Sb (4) (2-) and η(4)-Bi (4) (2-) ligands in M(2)(η(4)-E(4))(2) possess conflicting aromaticity (σ antiaromaticity and π aromaticity), which differs from the all-metal multiple aromatic unit Al (4) (2-). In addition, all of these M(2)(η(4)-E(4))(2) species are stable according to the dissociation energies of M(2)(η(4)-E(4))(2) → 2 M(η(4)-E(4)) and M(2)(η(4)-E(4))(2) → 2 M + 2E(4), and these stable species can be synthesized by two-step substitution reactions: CpZnZnCp + 2E (4) (2-) → [E(4)ZnZnE(4)](2-) + 2Cp(-) and [E(4)ZnZnE(4)](2-) + 2 M (2) (+) → E(4)MME(4) + 2Zn(+).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Antimony / chemistry
  • Bismuth / chemistry
  • Computer Simulation*
  • Coordination Complexes / chemistry*
  • Gallium / chemistry
  • Indium / chemistry
  • Models, Molecular*
  • Quantum Theory
  • Thermodynamics
  • Zinc / chemistry

Substances

  • Coordination Complexes
  • Indium
  • Antimony
  • Gallium
  • Zinc
  • Bismuth