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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Intramolecular Csp3-H Activation at a Platinum(IV) Center Resulting from O2 Activation: The Role of a
Juan Rueda-Espinosa1,2, Wen Zhou1, Jennifer A Love1,2
1Department of Chemistry, University of Calgary, 2500 University Dr. NW, Calgary, Alberta T2N 1N4, Canada.
Abstract:
Aerobic oxidation of a dimethylplatinum(II) complex featuring 1,1-di(2-pyridyl)ethanol as a supporting ligand leads to the formation of two unexpected PtIV complexes (in ∼1:1 ratio), neither of which results from direct oxidation typical for PtII centers supported by popular κ2-(N,N) ligands. While one product features an isomerized PtIV center stabilized by the κ3-(N,N,O) ligand coordination mode, surprisingly, the other product results from intramolecular activation of the ligand methyl fragment. Mechanistic studies, reactivity of model complexes, and DFT calculations reveal that the critical proton-responsive nature of the ligand allows formation of intermediates that result in a concerted metalation deprotonation (CMD)-like C-H activation at PtIV. To the best of our knowledge, this is the first mechanistic delineation of Csp3-H activation at PtIV, despite being known for other high-valent platinum group metal centers.
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