Oxidative Addition of a Mechanically Entrapped C(sp)–C(sp) Bond to a Rhodium(I) Pincer Complex

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.