Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis.
J Am Chem Soc
; 138(30): 9682-93, 2016 08 03.
Article
en En
| MEDLINE
| ID: mdl-27458778
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.
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MEDLINE
Asunto principal:
Compuestos Organoplatinos
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Revista:
J Am Chem Soc
Año:
2016
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Article