Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 30, Pages 9682-9693Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b05442
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Funding
- Office of Science, Office of Basic Energy Sciences and the Division of Chemical Sciences, Geosciences, and Biosciences of the U.S. Department of Energy at Lawrence Berkeley National Laboratory [DE-AC02-05CH11231]
- NIH National Institute of General Medical Sciences [R01 GM073932]
- NSF GRFP program
- ARCS foundation
- NSF GRFP [DGE 1106400]
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
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The scope and mechanism of the microenvironmentcatalyzed C(sp(3)) C(sp(3)) reductive elimination from transition metal complexes [Au(III), Pt(IV)] is explored. Experiments detailing the effect of structural perturbation of neutral and anionic spectator ligands, reactive alkyl ligands, solvent, and catalyst structure are disclosed. Indirect evidence for a coordinatively unsaturated encapsulated cationic intermediate is garnered via observation of several inactive donor arrested inclusion complexes, including a crystallographically characterized encapsulated Au(III) cation. Finally, based on stoichiometric experiments under catalytically relevant conditions, a detailed mechanism is outlined for the dual supramolecular and platinum catalyzed C C coupling between methyl iodide and tetramethyltin. Determination of major platinum species present under catalytic conditions and subsequent investigation of their chemistry reveals an unexpected interplay between cis trans isomerism and the suprarnolecular catalyst in a Pt(II)/Pt(IV) cycle, as well as several off-cycle reactions.
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