From gas-phase ionization energies to solution oxidation potentials: Dimolybdenum tetraformamidinate paddlewheel complexes

Laura O. Van Dorn, Susan C. Borowski, Dennis L. Lichtenberger

Research output: Research - peer-reviewArticle

  • 2 Citations

Abstract

The gas-phase ionization energies of a series of Mo2(DPhF)4 paddlewheel complexes (DPhF is the N,N′-diphenylformamidinate anion with p-CH3, p-Cl, m-Cl, p-CF3, or m-CF3 phenyl substituents) have been measured by ultraviolet photoelectron spectroscopy (UPS) and compared with the solution oxidation potentials measured by cyclic voltammetry (CV) reported by Ren and coworkers. A linear relationship was found between the gas-phase ionization energies and the solution oxidation potentials. Density functional theory (DFT) computations clarify the individual electronic and thermodynamic factors that contribute to the correlation. The metal-metal delta bond electron energy is the largest factor in determining the solution oxidation potential. The substituents shift the metal-metal orbital energies by changing the through-space field potential at the metals rather than by an inductive change in charge at the metals or orbital overlap effects. The cation solvation energies determine the extent that the potential shifts are attenuated in solution. The results show that substituent field effects and solvation have major roles in determining the dimetal redox chemistry even when the dimetal unit is protected from direct interaction with the substituent and the solvent.

LanguageEnglish (US)
Pages316-321
Number of pages6
JournalInorganica Chimica Acta
Volume424
DOIs
StatePublished - Jan 1 2015

Fingerprint

vapor phases
ionization
oxidation
metals
energy
Ionization potential
Oxidation
Metals
Gases
solvation
orbitals
shift
Solvation
ultraviolet spectroscopy
potential fields
photoelectron spectroscopy
electron energy
methylidyne
chemistry
density functional theory

Keywords

  • Cyclic voltammetry
  • Density functional theory
  • LFER
  • Metal-metal bonds
  • Photoelectron spectroscopy
  • Substituent effects

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

From gas-phase ionization energies to solution oxidation potentials : Dimolybdenum tetraformamidinate paddlewheel complexes. / Van Dorn, Laura O.; Borowski, Susan C.; Lichtenberger, Dennis L.

In: Inorganica Chimica Acta, Vol. 424, 01.01.2015, p. 316-321.

Research output: Research - peer-reviewArticle

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