Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in CH2Cl2

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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Abstract

Infrared spectroscopy has been used to determine the relative anion affinities in CH2Cl2 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- ∼ OClO3 -. A smaller series for L = AsPh3 displayed a similar trend, but with positions of NCS- and Cl- 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
StatePublished - 1988

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Rhodium
Carbon Monoxide
rhodium
affinity
Cations
anions
Ligands
cations
ligands
Anions
Equilibrium constants
trends
metathesis
infrared spectroscopy
triphenylphosphine
Infrared spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Araghizadeh, F., Branan, D. M., Hoffman, N. W., Jones, J. H., McElroy, E. A., Miller, N. C., ... Young, S. H. (1988). Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in CH2Cl2 Inorganic Chemistry, 27(21), 3752-3755.

Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in CH2Cl2 . / Araghizadeh, Farshid; Branan, Daniel M.; Hoffman, Norris W.; Jones, John H.; McElroy, E. Andrew; Miller, Nathan C.; Ramage, David L.; Salazar, Anna Battaglia; Young, Sidney H.

In: Inorganic Chemistry, Vol. 27, No. 21, 1988, p. 3752-3755.

Research output: Contribution to journalArticle

Araghizadeh, F, Branan, DM, Hoffman, NW, Jones, JH, McElroy, EA, Miller, NC, Ramage, DL, Salazar, AB & Young, SH 1988, 'Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in CH2Cl2 ', Inorganic Chemistry, vol. 27, no. 21, pp. 3752-3755.
Araghizadeh F, Branan DM, Hoffman NW, Jones JH, McElroy EA, Miller NC et al. Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in CH2Cl2 Inorganic Chemistry. 1988;27(21):3752-3755.
Araghizadeh, Farshid ; Branan, Daniel M. ; Hoffman, Norris W. ; Jones, John H. ; McElroy, E. Andrew ; Miller, Nathan C. ; Ramage, David L. ; Salazar, Anna Battaglia ; Young, Sidney H. / Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in CH2Cl2 In: Inorganic Chemistry. 1988 ; Vol. 27, No. 21. pp. 3752-3755.
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abstract = "Infrared spectroscopy has been used to determine the relative anion affinities in CH2Cl2 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- ∼ OClO3 -. A smaller series for L = AsPh3 displayed a similar trend, but with positions of NCS- and Cl- 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.",
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T1 - Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in CH2Cl2

AU - Araghizadeh, Farshid

AU - Branan, Daniel M.

AU - Hoffman, Norris W.

AU - Jones, John H.

AU - McElroy, E. Andrew

AU - Miller, Nathan C.

AU - Ramage, David L.

AU - Salazar, Anna Battaglia

AU - Young, Sidney H.

PY - 1988

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N2 - Infrared spectroscopy has been used to determine the relative anion affinities in CH2Cl2 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- ∼ OClO3 -. A smaller series for L = AsPh3 displayed a similar trend, but with positions of NCS- and Cl- 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.

AB - Infrared spectroscopy has been used to determine the relative anion affinities in CH2Cl2 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- ∼ OClO3 -. A smaller series for L = AsPh3 displayed a similar trend, but with positions of NCS- and Cl- 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.

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