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Experiments mixing the stable 16e 5-coordinate complexes [RhCp*Ar 2 ] (Cp* = C 5 Me 5 ; Ar = C 6 F 5 , C 6 F 3 Cl 2 -3,5) uncover fast aryl transmetalations. Unexpectedly, as supported computationally, these exchanges are not spontaneous, but catalyzed by minute amounts of 18e (μ-OH) 2 [RhCp*Ar] 2 as a source of 16e [RhCp*Ar(OH)]. The OH group is an amazingly efficient bridging partner to diminish the activation barrier of transmetalation.

Hidden aryl-exchange processes in stable 16e RhIII[RhCp*Ar2] complexes, and their unexpected transmetalation mechanism

Hidden aryl-exchange processes in stable 16e Rh^III[RhCp*Ar₂] complexes, and their unexpected transmetalation mechanism