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

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.

Recent advances in organophosphorus–chalcogen and organophosphorus–pincer based macrocyclic compounds and their metal complexes

“…Dalton Transactions macrocyclic phosphinite pincer ligand with bulky phosphorus substituents, as outlined in Scheme 32. 149 The rhodium(III)bis (alkynyl) product was trapped by reacting with CO or consumed through an irreversible reaction with dihydrogen throughout the selective hydrogenolysis of the C-C σ-bond (Scheme 32). The reaction of the Rh complex, trans-90b with Ar′C 2 MgCl•LiCl afforded bis-(alkynyl)carbonyl complex 95 which on decarbonylation with Me 3 NO yielded complex 96 (Scheme 32).…”

Rotaxane CoII Complexes as Field‐Induced Single‐Ion Magnets

“…Interlocked molecules [1–5] contain cavities within which donor atoms can be positioned to bind metal ions [6–13] . Indeed, some of the first observations of the properties of the mechanical bond, including its ability to kinetically stabilize metal complexes, [6, 14–18] were made by Sauvage and co‐workers over 30 years ago [19–21] . More recently, [22] we demonstrated that rotaxane‐based ligands can be used to produce complexes the non‐interlocked equivalent of which are inaccessible, including examples reminiscent of the distorted “entatic states” of metalloproteins, [23, 24] suggesting that interlocked ligands could allow engineering of the properties of metal ions.…”

The Fascinating Flexibility and Coordination Modes of a Pentamethylene Connected Macrocyclic CNC Pincer Ligand

“…Notably, Chaplin and coworkers showed very interesting examples of macrocyclic CNC ligands that contain alkyl tethers between 8 and 16 C-atoms [ 3 , 4 , 5 ]. Their transition metal complexes showed particular properties depending on the ring size [ 6 , 7 , 8 ], but no reactivity at the tether itself.…”