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>)CO], <b>10</b>. A brief discussion of
possible mechanisms is presented.