title: Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis.
abstract: The scope and mechanism of the microenvironment-catalyzed 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 supramolecular catalyst in a Pt(II)/Pt(IV) cycle, as well as several off-cycle reactions.
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory and Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Mark D
authors.initials: MD
authors.lastname: Levin
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory and Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: David M
authors.initials: DM
authors.lastname: Kaphan
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory and Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Cynthia M
authors.initials: CM
authors.lastname: Hong
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory and Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Robert G
authors.initials: RG
authors.lastname: Bergman
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory and Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Kenneth N
authors.initials: KN
authors.lastname: Raymond
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory and Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste
mesh_terms: D002384:Catalysis; D006046:Gold / Q000737:chemistry*; D006847:Hydrocarbons, Iodinated / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009944:Organoplatinum Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D006847:Hydrocarbons, Iodinated; D009944:Organoplatinum Compounds; D006046:Gold; C014055:methyl iodide