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

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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
Issue number13
Publication statusPublished - Jul 2 2018


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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