Interplay between solvent and counteranion stabilization of highly unsaturated rhodium(III) complexes: facile...

Abstraction of the chloride ligand from the PCN-based chloromethylrhodium complex 2 by AgX (X=BF(4)(-), CF(3)SO(3)(-)) or a direct C-C cleavage reaction of the PCN ligand 1 with [(coe)(2)Rh(solv)(n)](+)X(-) (coe=cyclooctene) lead to the formation of the coordinatively unsaturated rhodium(III) complexes 3. Compound 3 a (X=BF(4)(-)) exhibits a unique medium effect; the metal center is stabilized by reversible coordination of the bulky counteranion or solvent as a function of temperature. Reaction of [(PCN)Rh(CH(3))(Cl)] with AgBAr(f) in diethyl ether leads to an apparent rhodium(III) 14-electron complex 4, which is stabilized by reversible, weak coordination of a solvent molecule. This complex coordinates donors as weak as diethyl ether and dichloromethane. Upon substitution of the BF(4)(-) ion in [(PCN)Rh(CH(3))]BF(4) by the noncoordinating BAr(f)(-) ion in a noncoordinating medium, the resulting highly unsaturated intermediate undergoes a 1,2-metal-to-carbon methyl shift, followed by beta-hydrogen elimination, leading to the Rh-stabilized methylene arenium complex 5. This process represents a unique mild, dearomatization of the aromatic system induced by unsaturation.