Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu-H: Different Rate-Limiting Steps as a Function of Electrophilicity

Tran, Ba L.; Neisen, Benjamin D.; Speelman, Amy L.; Gunasekara, Thilina; Wiedner, Eric S.; Bullock, R. Morris

doi:10.1002/anie.201916406

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu-H: Different Rate-Limiting Steps as a Function of Electrophilicity

Journal Article · Wed Feb 05 04:00:00 EST 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201916406· OSTI ID:1645100

Tran, Ba L. ^[1]; Neisen, Benjamin D. ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis

In this paper, we report mechanistic studies on the insertion reactions of [(NHC)Cu(H)]₂ complexes with carbonyl substrates by UV-vis and ¹H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X-ray crystallography. The results of these comprehensive studies show that the insertion of Cu-H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu-H monomer from Cu-H dimer for more electrophilic substrates and hydride transfer from a transient Cu-H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu-hemiacetalate and Cu-hemiaminalate moieties from the insertion of an ester and amide into the Cu-H bond.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1645100

Alternate ID(s):: OSTI ID: 1633670

Report Number(s):: PNNL-SA-150267

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 22 Vol. 59; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu-H: Different Rate-Limiting Steps as a Function of Electrophilicity

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