Oxidative Addition of a Mechanically Entrapped C(sp)–C(sp) Bond to a Rhodium(I) Pincer Complex
Baptiste Leforestier, Matthew R. Gyton, Adrian B. Chaplin
Abstract
By use of a macrocyclic phosphinite pincer ligand and bulky substrate substituents, we demonstrate how the mechanical bond can be leveraged to promote the oxidative addition of an interlocked 1,3-diyne to a rhodium(I) center. The resulting rhodium(III) bis(alkynyl) product can be trapped out by reaction with carbon monoxide or intercepted through irreversible reaction with dihydrogen, resulting in selective hydrogenolysis of the C-C σ-bond.
Topics & Concepts
RhodiumPincer movementChemistryHydrogenolysisOxidative additionLigand (biochemistry)PhosphiniteCarbon monoxidePincer ligandSubstrate (aquarium)PhotochemistryMedicinal chemistryStereochemistryCatalysisOrganic chemistryBiochemistryOceanographyGeologyReceptorCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and Catalysis