om0008171_si_001.pdf (637.27 kB)
Conversion of Perfluorobenzyl Complexes of Rhodium to Fluorinated Oxarhodacycles
journal contribution
posted on 2000-12-14, 00:00 authored by Russell P. Hughes, Danielle C. Lindner, Louise M. Liable-Sands, Arnold L. RheingoldThe 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)CO], 10. A brief discussion of
possible mechanisms is presented.