Relative Affinities of Carbonyibis (triphenylphosphine) rhodium (I) and Related Cations for Anionic Ligands in CH2C12

Farshid Araghizadeh, Daniel M. Branan, Norris W. Hoffman, John H. Jones, E. Andrew McElroy, Nathan C. Miller, David L. Ramage, Anna Battaglia Salazar, Sidney H. Young

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32 Scopus citations

Abstract

Infrared spectroscopy has been used to determine the relative anion affinities in CH2C12 of Rh(PPh3)2(CO)+ and Rh(AsPh3)2(CO)+via measurement of equilibrium constants for the metatheses RhL2(CO)Y + PPN+Z- = RhL2(CO)Z + PPN+Y-. Observed for L = PPh3 was the anion affinity trend NCO- ≫ O2CMe- ~ O2CPh- ≫ F- ~ NCS- > Cl- > Br- > I- ≫ ONO2 ~ O2CCF3 - ≫ OTf- ~ OC103 -. A smaller series for L = AsPh3 displayed a similar trend, but with positions of NCS- and CI- reversed. For most anion pairs studied, the equilibrium lies so far to the left or right that only limits could be calculated, given the inherent experimental limitations. For L = PPh3, the equilibrium constant for replacement of the least preferred anion by the most can be inferred as > 1019. Rh(PCy3)2(CO)Cl and Rh(PCy3)2(CO)Z (Z = NCS, NCSe, O2CMe; but not F, O2CPh, and NCO) interact strongly in solution and thus limit study of that series.

Original languageEnglish (US)
Pages (from-to)3752-3755
Number of pages4
JournalInorganic Chemistry
Volume27
Issue number21
DOIs
StatePublished - Oct 1 1988

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Araghizadeh, F., Branan, D. M., Hoffman, N. W., Jones, J. H., McElroy, E. A., Miller, N. C., Ramage, D. L., Salazar, A. B., & Young, S. H. (1988). Relative Affinities of Carbonyibis (triphenylphosphine) rhodium (I) and Related Cations for Anionic Ligands in CH2C12. Inorganic Chemistry, 27(21), 3752-3755. https://doi.org/10.1021/ic00294a016