Synthesis of the First Family of Rhodium(I) Perfluoroalkyl Complexes from Rhodium(I) Fluoro Complexes<SUP>1</SUP>

The rhodium(I) fluoro complexes [RhF(COD)(PR<INF>3</INF>)] (R = Ph (<BO>1a</BO>), C<INF>6</INF>H<INF>4</INF>OMe-4 (<BO>1b</BO>), i-Pr (<BO>1d</BO>), Cy (<BO>1e</BO>); COD = 1,5-cyclooctadiene) react with Me<INF>3</INF>SiR<INF>F</INF> to afford the rhodium(I) perfluoroalkyl complexes [Rh(R<INF>F</INF>)(COD)(PR<INF>3</INF>)] (R<INF>F</INF> = CF<INF>3</INF>, R = Ph (<BO>2a</BO>), C<INF>6</INF>H<INF>4</INF>OMe-4 (<BO>2b</BO>), i-Pr (<BO>2d</BO>), Cy (<BO>2e</BO>); R<INF>F</INF> = n-C<INF>3</INF>F<INF>7</INF>, R = Ph (<BO>2c</BO>)), of which <BO>2a</BO>,<BO>c</BO> were isolated as pure solids. [Rh(CF<INF>3</INF>)(NBD)(PPh<INF>3</INF>)] (<BO>3</BO>) was prepared by reaction of <BO>2a</BO> with norbornadiene. The reactions of <BO>2a</BO>−<BO>c</BO> with 2,6-dimethylphenyl isocyanide (XyNC) or t-BuNC, in a 1:2 molar ratio, gave the compounds trans-[Rh(R<INF>F</INF>)(CNR‘)<INF>2</INF>(PR<INF>3</INF>)] (R<INF>F</INF> = CF<INF>3</INF>, R‘ = Xy, R = Ph (<BO>4a</BO>), C<INF>6</INF>H<INF>4</INF>OMe-4 (<BO>4b</BO>); R<INF>F</INF> = CF<INF>3</INF>, R‘ = t-Bu, R = Ph (<BO>4a</BO>‘); R<INF>F</INF> = n-C<INF>3</INF>F<INF>7</INF>, R‘ = Xy, R = Ph (<BO>4c</BO>)). The reactions of <BO>2a</BO>−<BO>c</BO> with an equimolar amount of XyNC gave mixtures containing complexes <BO>4a</BO>−<BO>c</BO> as the major products. The peroxo complexes [Rh(CF<INF>3</INF>)(η²-O<INF>2</INF>)(CNXy)<INF>2</INF>(PR<INF>3</INF>)], (R = Ph (<BO>7a</BO>), C<INF>6</INF>H<INF>4</INF>OMe-4 (<BO>7b</BO>)) were isolated by reacting O<INF>2</INF> with <BO>4a</BO>,<BO>b</BO>, respectively. The complexes [Rh(R<INF>F</INF>)(CNR‘)<INF>3</INF>(PR<INF>3</INF>)] (R<INF>F</INF> = CF<INF>3</INF>, R‘ = Xy, R = Ph (<BO>8a</BO>), C<INF>6</INF>H<INF>4</INF>OMe-4 (<BO>8b</BO>); R<INF>F</INF> = n-C<INF>3</INF>F<INF>7</INF>, R‘ = Xy, R = Ph (<BO>8c</BO>)) were obtained by reaction of <BO>2a</BO>−<BO>c</BO> with 3 equiv of XyNC. Formation of [Rh(CF<INF>3</INF>)(PPh<INF>3</INF>)(CO)<INF>3</INF>] (<BO>9</BO>) in the reaction of complex <BO>2a</BO> with CO was spectroscopically observed. The crystal structures of complexes <BO>4a</BO>, <BO>7a</BO>, and <BO>8a</BO> have been determined by single-crystal X-ray diffraction studies. The dynamic behavior in solution of the prepared complexes was studied by variable-temperature NMR.