Two hydrogen ligands on tetrairidium clusters: a relativistic density functional study

Phys Chem Chem Phys. 2006 Aug 7;8(29):3391-8. doi: 10.1039/b605484f. Epub 2006 Jun 23.

Abstract

Structural and energetic properties of Ir(4)H(2) have been determined by applying a relativistic density functional method. As previously obtained for Ir(4)H, terminal coordination of H ligands is preferred, in contrast to some other transition metals. Square-planar Ir(4) isomers with an H binding energy of up to 318 kJ mol(-1) per atom were determined as the most stable structures of Ir(4)H(2). Isomers with a tetrahedral or butterfly structure of the metal framework exhibit average H atom binding energies of up to approximately 300 kJ mol(-1). For all three types of isomers, a surprisingly large number of stable minima was identified. Unexpectedly, structural as well as energetic properties of Ir(4)H(2) complexes are very similar to Ir(4)H. Thus binding of an H atom to Ir(4) is only slightly affected by the presence of a second H ligand. In all cases examined, the reaction H(2)+ Ir(4)--> H(2)Ir(4) was found to be exothermic with reaction energies of up to 170 kJ mol(-1).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Computer Simulation
  • Electrons
  • Energy Transfer
  • Hydrogen / chemistry*
  • Hydrogen Bonding
  • Iridium / chemistry*
  • Isomerism
  • Ligands
  • Models, Chemical*
  • Models, Molecular*
  • Molecular Conformation
  • Quantum Theory

Substances

  • Ligands
  • Iridium
  • Hydrogen