Direct Detection of Pt(IV) Phenyl Complexes upon Intermolecular Oxidative Addition of Aryl Halides and Selective Csp3–I versus Csp2–Csp3 and Csp3–Csp3 Bonds Reductive Elimination from N-Heterocyclic Carbene Pt(IV) Phenyl Complexes
Nan Zhang, Weiying He, Kristof M. Altus, Brian O. Patrick, Benjamin S. Gelfand, Pierre Kennepohl, Jennifer A. Love
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引用次数: 0
Abstract
Reaction of a chelating N-heterocyclic carbene Pt(II) dimethyl complex with phenyl iodide and excess KI results in the direct detection of a Pt(IV) phenyl intermediate by 1H NMR spectroscopy. This finding provides experimental evidence that the reaction between Pt(II) dimethyl complexes and aryl halides proceeds via a concerted oxidative addition (OA) mechanism. Additionally, we report on the selective reductive elimination (RE) of Csp3–I vs Csp2–Csp3 and Csp3–Csp3 bonds. Lastly, OA, different RE pathways, and reactivity of different isomers were investigated by computational methods that are consistent with experimental observations. We believe that these results have important implications for the development of new Pt-catalyzed transformations.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.