Calorimetric study of the lewis acid properties of coordinatively unsaturated organoiridium(III) species

T. W. Leung; M. J. Hintz; L. T. Chan; A. D. Sherry; D. M. Blake

doi:10.1021/ic50176a037

Calorimetric study of the lewis acid properties of coordinatively unsaturated organoiridium(III) species

T. W. Leung, M. J. Hintz, L. T. Chan, A. D. Sherry, D. M. Blake

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Abstract

The Lewis acid character of a series of coordinatively unsaturated iridium(III) complexes of the type {IrCl₂R[P(C₆H₅)₃] ₂| (R is C(O)CF_nH_3-n (n = 1, 2, or 3), -S(O)₂R′ (R′ = CH₃, C₂H₅, or CF₃), or CH₃) has been studied by calorimetric and spectroscopic methods. Enthalpy data for addition of pyridine as a function of R are interpreted in terms of a trans influence series for the R groups. This thermochemical trans influence series is compared with that derived from the trends in iridium-chlorine stretching frequencies in model compounds having R trans to Cl. The enthalpy change and equilibrium constant for pyridine addition to the complex in which R = C(O)CF₃ were determined in six solvents. The trends in enthalpy changes and equilibrium constants for addition of a series of ten bases to the trifluoroacetyl complex in methylene chloride are interpreted in terms of base strength and steric factors. The enthalpy change for pyridine addition to |IrClXCH₃ [P(C₆H₅)₃] ₂| (X = Cl, Br, -NCO, NO₂, or CH₃CO₂) in methylene chloride reveals that the cis influence of X is low. Representative examples of the octahedral adducts {IrCl₂R[P(C₆H₅)₃]₂. Bj have been isolated and characterized. In each case the base B is found to add stereospecifically trans to the substituent R.

Original language	English (US)
Pages (from-to)	2606-2612
Number of pages	7
Journal	Inorganic Chemistry
Volume	16
Issue number	10
DOIs	https://doi.org/10.1021/ic50176a037
State	Published - Oct 1 1977

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{e857462b14414661a5917bd7eb85c53f,

title = "Calorimetric study of the lewis acid properties of coordinatively unsaturated organoiridium(III) species",

abstract = "The Lewis acid character of a series of coordinatively unsaturated iridium(III) complexes of the type {IrCl2R[P(C6H5)3] 2| (R is C(O)CFnH3-n (n = 1, 2, or 3), -S(O)2R′ (R′ = CH3, C2H5, or CF3), or CH3) has been studied by calorimetric and spectroscopic methods. Enthalpy data for addition of pyridine as a function of R are interpreted in terms of a trans influence series for the R groups. This thermochemical trans influence series is compared with that derived from the trends in iridium-chlorine stretching frequencies in model compounds having R trans to Cl. The enthalpy change and equilibrium constant for pyridine addition to the complex in which R = C(O)CF3 were determined in six solvents. The trends in enthalpy changes and equilibrium constants for addition of a series of ten bases to the trifluoroacetyl complex in methylene chloride are interpreted in terms of base strength and steric factors. The enthalpy change for pyridine addition to |IrClXCH3 [P(C6H5)3] 2| (X = Cl, Br, -NCO, NO2, or CH3CO2) in methylene chloride reveals that the cis influence of X is low. Representative examples of the octahedral adducts {IrCl2R[P(C6H5)3]2. Bj have been isolated and characterized. In each case the base B is found to add stereospecifically trans to the substituent R.",

author = "Leung, {T. W.} and Hintz, {M. J.} and Chan, {L. T.} and Sherry, {A. D.} and Blake, {D. M.}",

year = "1977",

month = oct,

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doi = "10.1021/ic50176a037",

language = "English (US)",

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journal = "Inorganic Chemistry",

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T1 - Calorimetric study of the lewis acid properties of coordinatively unsaturated organoiridium(III) species

AU - Leung, T. W.

AU - Hintz, M. J.

AU - Chan, L. T.

AU - Sherry, A. D.

AU - Blake, D. M.

PY - 1977/10/1

Y1 - 1977/10/1

N2 - The Lewis acid character of a series of coordinatively unsaturated iridium(III) complexes of the type {IrCl2R[P(C6H5)3] 2| (R is C(O)CFnH3-n (n = 1, 2, or 3), -S(O)2R′ (R′ = CH3, C2H5, or CF3), or CH3) has been studied by calorimetric and spectroscopic methods. Enthalpy data for addition of pyridine as a function of R are interpreted in terms of a trans influence series for the R groups. This thermochemical trans influence series is compared with that derived from the trends in iridium-chlorine stretching frequencies in model compounds having R trans to Cl. The enthalpy change and equilibrium constant for pyridine addition to the complex in which R = C(O)CF3 were determined in six solvents. The trends in enthalpy changes and equilibrium constants for addition of a series of ten bases to the trifluoroacetyl complex in methylene chloride are interpreted in terms of base strength and steric factors. The enthalpy change for pyridine addition to |IrClXCH3 [P(C6H5)3] 2| (X = Cl, Br, -NCO, NO2, or CH3CO2) in methylene chloride reveals that the cis influence of X is low. Representative examples of the octahedral adducts {IrCl2R[P(C6H5)3]2. Bj have been isolated and characterized. In each case the base B is found to add stereospecifically trans to the substituent R.

AB - The Lewis acid character of a series of coordinatively unsaturated iridium(III) complexes of the type {IrCl2R[P(C6H5)3] 2| (R is C(O)CFnH3-n (n = 1, 2, or 3), -S(O)2R′ (R′ = CH3, C2H5, or CF3), or CH3) has been studied by calorimetric and spectroscopic methods. Enthalpy data for addition of pyridine as a function of R are interpreted in terms of a trans influence series for the R groups. This thermochemical trans influence series is compared with that derived from the trends in iridium-chlorine stretching frequencies in model compounds having R trans to Cl. The enthalpy change and equilibrium constant for pyridine addition to the complex in which R = C(O)CF3 were determined in six solvents. The trends in enthalpy changes and equilibrium constants for addition of a series of ten bases to the trifluoroacetyl complex in methylene chloride are interpreted in terms of base strength and steric factors. The enthalpy change for pyridine addition to |IrClXCH3 [P(C6H5)3] 2| (X = Cl, Br, -NCO, NO2, or CH3CO2) in methylene chloride reveals that the cis influence of X is low. Representative examples of the octahedral adducts {IrCl2R[P(C6H5)3]2. Bj have been isolated and characterized. In each case the base B is found to add stereospecifically trans to the substituent R.

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Calorimetric study of the lewis acid properties of coordinatively unsaturated organoiridium(III) species

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