Conversion of perfluorobenzyl complexes of rhodium to fluorinated oxarhodacycles

Article abstract of DOI:10.1021/om0008171

The perfluorobenzylrhodium complex [Cp*Rh(CO)(CF₂C₆F₅)(I)], 1 (Cp* = C₅Me₅), reacts with N-methylmorpholine-N-oxide (NMO) with loss of CO₂ and formation of the iodo-bridged dimer [Cp*Rh(μ₂-I)(CF₂C₆F₅)] ₂, 5, which has been characterized by X-ray crystallography. While attempts to prepare hydroxo complexes by reaction of [Cp*Rh(PMe₃)(CF₂C₆F₅)(I)], 3, with sources of hydroxide were unsuccessful, treatment of 3 with moist silver oxide affords the oxametallacycle [Cp*(PMe₃)RhO(C₆F₄)CF₂, 9, which undergoes rapid hydrolysis of the α-CF₂ group by adventitious moisture to afford the crystallographically characterized analogue [Cp*(PMe₃)RhO(C₆F₄)C=O], 10. A brief discussion of possible mechanisms is presented.