Dimers of Nineteen-Electron Sandwich Compounds: An Electrochemical Study of the Kinetics of Their Formation

Karttikay Moudgil, Megan A. Mann, Chad Risko, Lawrence A. Bottomley, Seth R. Marder, Stephen Barlow

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8 Scopus citations

Abstract

(Chemical Equation Presented). Rate constants for the dimerization of FeCp∗C6H6, RuCp∗mes, RhCp2, RhCp∗Cp, and IrCp∗Cp (Cp∗ = pentamethylcyclopentadienyl; mes = 1,3,5-trimethylbenzene; Cp = cyclopentadienyl) have been investigated by cyclic voltammetry. Rates increased in the order FeCp∗C6H6 蠐 RhCp∗Cp ∼ RhCp2 < RuCp∗mes and IrCp∗Cp. The difference in rates between the Rh compounds and the Ru and Ir species is consistent with the thermodynamic driving forces for dimerization estimated from DFT calculations. However, the sluggish dimerization of FeCp∗C6H6 cannot be rationalized with purely thermodynamic considerations and may be attributable to the very different spin-density distribution in this species. On the basis of the activation parameters for dimerization, determined by variable temperature cyclic voltammetry, and those previously determined for dissociation of the corresponding dimer, the free energy of dimerization for the RhCp∗Cp monomer was estimated to be -43 kJ mol-1, and the effective redox potential for the RhCp∗Cp+/ 0.5(RhCp∗Cp)2 couple was estimated as -1.84 V vs FeCp2+/FeCp2.

Original languageEnglish
Pages (from-to)3706-3712
Number of pages7
JournalOrganometallics
Volume34
Issue number15
DOIs
StatePublished - Aug 10 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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