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<p>Density functional theory (DFT) studies are carried out to investigate the hydride transfer mechanism in the transfer hydrogenation of carbonyl compounds catalysed by Ir–Cp* azocarboxamide complexes. The calculations show that the asynchronous type of outer sphere metal hydridic pathway is energetically more favourable than the inner-sphere ligand-assisted hydridic route. Activation energy barriers for each step of different pathways are calculated using DFT, including the outer sphere hydridic route and inner sphere ligand-assisted route, highlighting how the hydridic route and metal alkoxide ligand hydridic route play an interesting role in determining the best-suited pathway. These computational outcomes portray the key electronic and steric factors that govern catalytic activity in azocarboxamide-based Ir complexes, which correlate with the experimental study.</p> Graphical abstract <p><i>Synopsis.</i> DFT analyses of Ir–Cp* azocarboxamide complexes for the transfer hydrogenation show that the asynchronous hydridic pathway is energetically preferred over the inner-sphere ligand-assisted method. The catalytic path is controlled by electronic parameters, energy barriers, which show the importance of hydridic and alkoxide-assisted pathways in agreement with the results.</p>

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Ligand-assisted transfer hydrogenation of ketones and aldehydes via iridium azocarboxamide catalyst: A DFT-based mechanistic investigation

  • 期刊论文

  • 发表日期：

    2026年4月4日

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  • Suravi Das,
  • Poulami Pal,
  • Gourab Kanti Das

摘要

Density functional theory (DFT) studies are carried out to investigate the hydride transfer mechanism in the transfer hydrogenation of carbonyl compounds catalysed by Ir–Cp* azocarboxamide complexes. The calculations show that the asynchronous type of outer sphere metal hydridic pathway is energetically more favourable than the inner-sphere ligand-assisted hydridic route. Activation energy barriers for each step of different pathways are calculated using DFT, including the outer sphere hydridic route and inner sphere ligand-assisted route, highlighting how the hydridic route and metal alkoxide ligand hydridic route play an interesting role in determining the best-suited pathway. These computational outcomes portray the key electronic and steric factors that govern catalytic activity in azocarboxamide-based Ir complexes, which correlate with the experimental study.

Graphical abstract

Synopsis. DFT analyses of Ir–Cp* azocarboxamide complexes for the transfer hydrogenation show that the asynchronous hydridic pathway is energetically preferred over the inner-sphere ligand-assisted method. The catalytic path is controlled by electronic parameters, energy barriers, which show the importance of hydridic and alkoxide-assisted pathways in agreement with the results.