### Abstract

DFT methods are used to calculate the ionization energy (IE) and electron affinity (EA) trends in a series of pincer ligated d^{8}-Ir(^{tBu4}PXCXP) complexes (1-X), where C is a 2,6-disubstituted phenyl ring with X = O, NH, CH_{2}, BH, S, PH, SiH_{2}, and GeH_{2}. Both C_{2v} and C_{2} geometries are considered. Two distinct σ-type (^{2}A_{1} or ^{2}A) and π-type (^{2}B_{1} or ^{2}B) 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 H_{2} addition to 1-X. Two closed shell singlet states differentiated in the C_{2} point group by the d^{6}-electon configuration are investigated for the five-coordinate Ir(III) dihydride product. One electronic state has a d^{6}-(a)^{2}(b)^{2}(b)^{2} configuration and a square pyramidal geometry, the other a d^{6}-(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 H_{2} addition and either the IEs or EAs. To better understand the origin of the computed trends, the thermodynamics of H_{2} 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-CH_{2} can have very similar reaction energies for H_{2} 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 H_{2} addition leading to the Y-product.

Original language | English |
---|---|

Pages (from-to) | 12348-12359 |

Number of pages | 12 |

Journal | Inorganic Chemistry |

Volume | 53 |

Issue number | 23 |

DOIs | |

Publication status | Published - Dec 1 2014 |

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### ASJC Scopus subject areas

- Inorganic Chemistry
- Physical and Theoretical Chemistry

### Cite this

^{8}-Ir(

^{tBu4}PXCXP) complexes: Implications for the thermodynamics of oxidative H

_{2}addition.

*Inorganic Chemistry*,

*53*(23), 12348-12359. https://doi.org/10.1021/ic5015829

**Calculation of ionization energy, electron affinity, and hydride affinity trends in pincer-ligated d ^{8}-Ir(^{tBu4}PXCXP) complexes : Implications for the thermodynamics of oxidative H_{2} addition.** / Baroudi, Abdulkader; El-Hellani, Ahmad; Bengali, Ashfaq A.; Goldman, Alan S; Hasanayn, Faraj.

Research output: Contribution to journal › Article

^{8}-Ir(

^{tBu4}PXCXP) complexes: Implications for the thermodynamics of oxidative H

_{2}addition',

*Inorganic Chemistry*, vol. 53, no. 23, pp. 12348-12359. https://doi.org/10.1021/ic5015829

^{8}-Ir(

^{tBu4}PXCXP) complexes: Implications for the thermodynamics of oxidative H

_{2}addition. Inorganic Chemistry. 2014 Dec 1;53(23):12348-12359. https://doi.org/10.1021/ic5015829

}

TY - JOUR

T1 - Calculation of ionization energy, electron affinity, and hydride affinity trends in pincer-ligated d8-Ir(tBu4PXCXP) complexes

T2 - Implications for the thermodynamics of oxidative H2 addition

AU - Baroudi, Abdulkader

AU - El-Hellani, Ahmad

AU - Bengali, Ashfaq A.

AU - Goldman, Alan S

AU - Hasanayn, Faraj

PY - 2014/12/1

Y1 - 2014/12/1

N2 - 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.

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.

UR - http://www.scopus.com/inward/record.url?scp=84914145414&partnerID=8YFLogxK

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U2 - 10.1021/ic5015829

DO - 10.1021/ic5015829

M3 - Article

VL - 53

SP - 12348

EP - 12359

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 23

ER -