10.1021/om0008171.s001 Russell P. Hughes Russell P. Hughes Danielle C. Lindner Danielle C. Lindner Louise M. Liable-Sands Louise M. Liable-Sands Arnold L. Rheingold Arnold L. Rheingold Conversion of Perfluorobenzyl Complexes of Rhodium to Fluorinated Oxarhodacycles American Chemical Society 2000 C 5 Fluorinated Oxarhodacycles CF silver oxide Perfluorobenzyl Complexes CO 2 hydroxo complexes NMO Cp 2000-12-14 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Conversion_of_Perfluorobenzyl_Complexes_of_Rhodium_to_Fluorinated_Oxarhodacycles/3764415 The perfluorobenzylrhodium complex [Cp*Rh(CO)(CF<sub>2</sub>C<sub>6</sub>F<sub>5</sub>)(I)], <b>1 </b>(Cp* = C<sub>5</sub>Me<sub>5</sub>), reacts with <i>N</i>-methylmorpholine-<i>N</i>-oxide (NMO) with loss of CO<sub>2</sub> and formation of the iodo-bridged dimer [Cp*Rh(μ<sub>2</sub>-I)(CF<sub>2</sub>C<sub>6</sub>F<sub>5</sub>)]<sub>2</sub>, <b>5</b>, which has been characterized by X-ray crystallography. While attempts to prepare hydroxo complexes by reaction of [Cp*Rh(PMe<sub>3</sub>)(CF<sub>2</sub>C<sub>6</sub>F<sub>5</sub>)(I)], <b>3</b>, with sources of hydroxide were unsuccessful, treatment of <b>3 </b>with moist silver oxide affords the oxametallacycle [Cp*(PMe<sub>3</sub>)RhO(C<sub>6</sub>F<sub>4</sub>)CF<sub>2</sub>], <b>9</b>, which undergoes rapid hydrolysis of the α-CF<sub>2</sub> group by adventitious moisture to afford the crystallographically characterized analogue [Cp*(PMe<sub>3</sub>)RhO(C<sub>6</sub>F<sub>4</sub>)CO], <b>10</b>. A brief discussion of possible mechanisms is presented.