Metal-metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes

J Mol Model. 2012 May;18(5):1961-8. doi: 10.1007/s00894-011-1225-y. Epub 2011 Aug 26.

Abstract

Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amines / chemistry*
  • Coordination Complexes / chemistry*
  • Crystallography, X-Ray
  • Electrons
  • Models, Molecular
  • Molecular Structure
  • Pyridines / chemistry*
  • Quantum Theory
  • Ruthenium / chemistry*

Substances

  • Amines
  • Coordination Complexes
  • Pyridines
  • Ruthenium