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Tandem Oligomerization-Hydrogenation Using Brønsted Acidic Iridium Hydride Catalysts

Title: Tandem Oligomerization-Hydrogenation Using Brønsted Acidic Iridium Hydride Catalysts
Authors: Austin J. Leitgeb; Scott M. Chapp; Caleb D. Fast; Kathryn E. Fink; Nathan D. Schley
Publication Year: 2025
Collection: The University of Auckland: Figshare
Subject Terms: Biophysics; Biochemistry; Microbiology; Molecular Biology; Biotechnology; Infectious Diseases; Biological Sciences not elsewhere classified; Chemical Sciences not elsewhere classified; mechanistic experiments argue; gasoline additive isooctane; cationic hydride precursor; cationic oligomerization; tandem oligomerization; proton transfer; olefin substrate; major product; isobutene competes; ionic mechanism; hydrogenation sequence; direct reduction; dihydrogen heterolysis
Description: Cationic iridium complexes bearing the tris[3,5-bis(trifluoromethyl)phenyl]phosphine ligand unexpectedly give acidic metal hydrides. Net-dihydrogen heterolysis at such complexes provides hydrogenation catalysis by an ionic mechanism. The direct reduction of isobutene competes with cationic oligomerization to give the gasoline additive isooctane (2,4,4-trimethylpentane) as a major product of a tandem oligomerization/hydrogenation sequence. Mechanistic experiments argue for the role of neutral iridium hydrides generated by the proton transfer of a cationic hydride precursor to an olefin substrate.
Document Type: article in journal/newspaper
Language: unknown
DOI: 10.1021/acs.organomet.5c00160.s001
Availability: https://doi.org/10.1021/acs.organomet.5c00160.s001; https://figshare.com/articles/journal_contribution/Tandem_Oligomerization-Hydrogenation_Using_Br_nsted_Acidic_Iridium_Hydride_Catalysts/29538621
Rights: CC BY-NC 4.0
Accession Number: edsbas.3376DFC3
Database: BASE