Calculation of ionization energy, electron affinity, and hydride affinity trends in pincer-ligated d8-Ir(tBu4PXCXP) complexes

Implications for the thermodynamics of oxidative H2 addition

Abdulkader Baroudi, Ahmad El-Hellani, Ashfaq A. Bengali, Alan S Goldman, Faraj Hasanayn

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

DFT methods are used to calculate the ionization energy (IE) and electron affinity (EA) trends in a series of pincer ligated d8-Ir(tBu4PXCXP) complexes (1-X), where C is a 2,6-disubstituted phenyl ring with X = O, NH, CH2, BH, S, PH, SiH2, and GeH2. Both C2v and C2 geometries are considered. Two distinct σ-type (2A1 or 2A) and π-type (2B1 or 2B) electronic states are calculated for each of the free radical cation and anion. The results exhibit complex trends, but can be satisfactorily accounted for by invoking a combination of electronegativity and specific π-orbital effects. The calculations are also used to study the effects of varying X on the thermodynamics of oxidative H2 addition to 1-X. Two closed shell singlet states differentiated in the C2 point group by the d6-electon configuration are investigated for the five-coordinate Ir(III) dihydride product. One electronic state has a d6-(a)2(b)2(b)2 configuration and a square pyramidal geometry, the other a d6-(a)2(b)2(a)2 configuration with a distorted-Y trigonal bipyramidal geometry. No simple correlations are found between the computed reaction energies of H2 addition and either the IEs or EAs. To better understand the origin of the computed trends, the thermodynamics of H2 addition are analyzed using a cycle of hydride and proton addition steps. The analysis highlights the importance of the electron and hydride affinities, which are not commonly used in rationalizing trends of oxidative addition reactions. Thus, different complexes such as 1-O and 1-CH2 can have very similar reaction energies for H2 addition arising from opposing hydride and proton affinity effects. Additional calculations on methane C-H bond addition to 1-X afford reaction and activation energy trends that correlate with the reaction energies of H2 addition leading to the Y-product.

Original languageEnglish
Pages (from-to)12348-12359
Number of pages12
JournalInorganic Chemistry
Volume53
Issue number23
DOIs
Publication statusPublished - Dec 1 2014

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Electron affinity
Ionization potential
electron affinity
Hydrides
hydrides
affinity
Electronic states
Thermodynamics
trends
ionization
thermodynamics
Geometry
Protons
Point groups
Electronegativity
Addition reactions
Methane
Discrete Fourier transforms
Free Radicals
Anions

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Calculation of ionization energy, electron affinity, and hydride affinity trends in pincer-ligated d8-Ir(tBu4PXCXP) complexes : Implications for the thermodynamics of oxidative H2 addition. / Baroudi, Abdulkader; El-Hellani, Ahmad; Bengali, Ashfaq A.; Goldman, Alan S; Hasanayn, Faraj.

In: Inorganic Chemistry, Vol. 53, No. 23, 01.12.2014, p. 12348-12359.

Research output: Contribution to journalArticle

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abstract = "DFT methods are used to calculate the ionization energy (IE) and electron affinity (EA) trends in a series of pincer ligated d8-Ir(tBu4PXCXP) complexes (1-X), where C is a 2,6-disubstituted phenyl ring with X = O, NH, CH2, BH, S, PH, SiH2, and GeH2. Both C2v and C2 geometries are considered. Two distinct σ-type (2A1 or 2A) and π-type (2B1 or 2B) electronic states are calculated for each of the free radical cation and anion. The results exhibit complex trends, but can be satisfactorily accounted for by invoking a combination of electronegativity and specific π-orbital effects. The calculations are also used to study the effects of varying X on the thermodynamics of oxidative H2 addition to 1-X. Two closed shell singlet states differentiated in the C2 point group by the d6-electon configuration are investigated for the five-coordinate Ir(III) dihydride product. One electronic state has a d6-(a)2(b)2(b)2 configuration and a square pyramidal geometry, the other a d6-(a)2(b)2(a)2 configuration with a distorted-Y trigonal bipyramidal geometry. No simple correlations are found between the computed reaction energies of H2 addition and either the IEs or EAs. To better understand the origin of the computed trends, the thermodynamics of H2 addition are analyzed using a cycle of hydride and proton addition steps. The analysis highlights the importance of the electron and hydride affinities, which are not commonly used in rationalizing trends of oxidative addition reactions. Thus, different complexes such as 1-O and 1-CH2 can have very similar reaction energies for H2 addition arising from opposing hydride and proton affinity effects. Additional calculations on methane C-H bond addition to 1-X afford reaction and activation energy trends that correlate with the reaction energies of H2 addition leading to the Y-product.",
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AB - DFT methods are used to calculate the ionization energy (IE) and electron affinity (EA) trends in a series of pincer ligated d8-Ir(tBu4PXCXP) complexes (1-X), where C is a 2,6-disubstituted phenyl ring with X = O, NH, CH2, BH, S, PH, SiH2, and GeH2. Both C2v and C2 geometries are considered. Two distinct σ-type (2A1 or 2A) and π-type (2B1 or 2B) electronic states are calculated for each of the free radical cation and anion. The results exhibit complex trends, but can be satisfactorily accounted for by invoking a combination of electronegativity and specific π-orbital effects. The calculations are also used to study the effects of varying X on the thermodynamics of oxidative H2 addition to 1-X. Two closed shell singlet states differentiated in the C2 point group by the d6-electon configuration are investigated for the five-coordinate Ir(III) dihydride product. One electronic state has a d6-(a)2(b)2(b)2 configuration and a square pyramidal geometry, the other a d6-(a)2(b)2(a)2 configuration with a distorted-Y trigonal bipyramidal geometry. No simple correlations are found between the computed reaction energies of H2 addition and either the IEs or EAs. To better understand the origin of the computed trends, the thermodynamics of H2 addition are analyzed using a cycle of hydride and proton addition steps. The analysis highlights the importance of the electron and hydride affinities, which are not commonly used in rationalizing trends of oxidative addition reactions. Thus, different complexes such as 1-O and 1-CH2 can have very similar reaction energies for H2 addition arising from opposing hydride and proton affinity effects. Additional calculations on methane C-H bond addition to 1-X afford reaction and activation energy trends that correlate with the reaction energies of H2 addition leading to the Y-product.

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