Activation, Deactivation and Reversibility in a Series of Homogeneous Iridium Dehydrogenation Catalysts

Sharninghausen, Liam S.; Crabtree, Robert H.

doi:10.1002/ijch.201700048

Activation, Deactivation and Reversibility in a Series of Homogeneous Iridium Dehydrogenation Catalysts

Journal Article · Thu Aug 10 00:00:00 EDT 2017 · Israel Journal of Chemistry

DOI:https://doi.org/10.1002/ijch.201700048· OSTI ID:1374669

Sharninghausen, Liam S. ^[1]; Crabtree, Robert H. ^[1]

Yale Chemistry Department 225 Prospect St New Haven, CT 06520-8107

Abstract

Dehydrogenation is a sustainable form of oxidation catalysis, as it avoids any primary oxidant and the waste that would accompany it. Homogeneous catalyst design for this reaction is delicate: the catalyst must have a sufficient H ₂ affinity to abstract two hydrogen atoms from the substrate but not so much affinity as to fail to release them as free H ₂ . N‐Heterocyclic carbene (NHC) ligands achieve this balancing act in a series of iridium catalysts based on the Ir(IMe) ₂ motif (IMe=N,N′‐dimethylimidazol‐2‐ylidene). Catalyst design also needs to account for mechanistic points outside of the catalytic cycle itself. To enter the cycle, there is often an initial precatalyst activation process, and elucidating this can lead to optimization of both precatalyst and reaction conditions. To leave the cycle, we can have reversible formation of off‐cycle species as well as an irreversible catalyst deactivation step. In our Cp*Ir(IMe) ₂ Cl precatalyst for dehydrogenative oxidation, Cp* is lost in the activation step. This suggested moving to a catalyst precursor lacking the Cp*, [Ir(IMe) ₂ (CO) ₂ ] ⁺ . Catalyst deactivation produces a series of unusual cluster cations such as [Ir ₆ (IMe) ₈ (CO) ₂ H ₁₄ ] ²⁺ . Among applications, dehydrogenative oxidation can be useful in upgrading of biomass glycerol by conversion to lactate, as a part of hydrogen borrowing chemistry and in reversible hydrogenation/dehydrogenation for H ₂ storage.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-84ER13297; SC0001298

OSTI ID:: 1374669

Alternate ID(s):: OSTI ID: 1537570

Journal Information:: Israel Journal of Chemistry, Journal Name: Israel Journal of Chemistry Journal Issue: 10-11 Vol. 57; ISSN 0021-2148

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Israel

Language:: English

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