H2 Addition to Pincer Iridium Complexes Yielding trans-Dihydride Products: Unexpected Correlations of Bond Strength with Bond Length and Vibrational Frequencies

Boushra S. Omar, Josephina Mallah, Mohamad Ataya, Bo Li, Xiaoguang Zhou, Santanu Malakar, Alan S Goldman, Faraj Hasanayn

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

R4PONOP-Ir-Me (R1) and R4POCOP-Ir-CO (R2), R = tBu or iPr, are known to undergo acid-catalyzed oxidative addition of H2 that yields octahedral products with two hydrides in a trans-configuration. We use density functional theory to study the free energies (?Gtrans) and equilibrium isotope effects (EIEtrans) for H2/D2 addition to R1, R2, and related complexes for R = tBu, iPr, and Me. For a given R, reaction of R1 is ∼5 kcal/mol more exergonic than R2. For a given subclass of complexes, ?Gtrans is more exergonic for the smaller R. The computed values of ?Gtrans vary between +5.1 and -17.4 kcal/mol. EIEtrans varies between 0.78 and 1.22. Counterintuitively, it is the less-exergonic reactions that afford products with shorter Ir-H bonds, greater symmetric and asymmetric trans-Ir-(H)2 stretching vibrational frequencies, and more inverse EIEtrans. This disparity is amplified in Me4PONOP-Os-CO, where ?Gtrans is -35.2 kcal/mol, yet the Os-H bonds are long, and the Os-H vibrational frequencies are low as compared with the Ir-H bonds, and EIEtrans is high (1.20). Attempts are made to account for the inverted bond strength-bond length correlation based on the hydricity of the products and the total negative charge on the trans-Ir(H)2 unit as computed using the Quantum Theory of Atoms in Molecules.

Original languageEnglish
Pages (from-to)7516-7523
Number of pages8
JournalInorganic Chemistry
Volume57
Issue number13
DOIs
Publication statusPublished - Jul 2 2018

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Iridium
dihydrides
Bond length
Vibrational spectra
Carbon Monoxide
iridium
Quantum theory
products
Hydrides
Isotopes
Free energy
Stretching
Density functional theory
quantum theory
Atoms
isotope effect
Molecules
hydrides
Acids
free energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

H2 Addition to Pincer Iridium Complexes Yielding trans-Dihydride Products : Unexpected Correlations of Bond Strength with Bond Length and Vibrational Frequencies. / Omar, Boushra S.; Mallah, Josephina; Ataya, Mohamad; Li, Bo; Zhou, Xiaoguang; Malakar, Santanu; Goldman, Alan S; Hasanayn, Faraj.

In: Inorganic Chemistry, Vol. 57, No. 13, 02.07.2018, p. 7516-7523.

Research output: Contribution to journalArticle

Omar, Boushra S. ; Mallah, Josephina ; Ataya, Mohamad ; Li, Bo ; Zhou, Xiaoguang ; Malakar, Santanu ; Goldman, Alan S ; Hasanayn, Faraj. / H2 Addition to Pincer Iridium Complexes Yielding trans-Dihydride Products : Unexpected Correlations of Bond Strength with Bond Length and Vibrational Frequencies. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 13. pp. 7516-7523.
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AU - Ataya, Mohamad

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