Synthetic, Thermochemical, and Catalytic Studies of Fluorinated Tertiary Phosphine Ligands R<sub>2</sub>PR<sub>f</sub> [R = Cy, Ph, <sup>i</sup>Pr; R<sub>f</sub> = CH‘<sub>2</sub>CH<sub>2</sub>(CF<sub>2</sub>)<sub>5</sub>CF<sub>3</sub>] in Rhodium Systems
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The fluoroalkylphosphine compounds PR2Rf (R = Cy (1); iPr (2); Rf = CH2CH2(CF2)5CF3) have been prepared from the reactions of the Grignard reagent IMgRf and appropriate ClPR2 (R = Cy, iPr). The fluorinated phosphine ligands [PR2Rf (R = Cy (1); iPr (2); Ph (3); Rf = CH2CH2(CF2)5CF3] react with [Rh(CO)2Cl]2 to yield the corresponding [Rh(CO)Cl(PR2Rf)2] (R = Cy (4); iPr (5); Ph (6)) complexes. Infrared studies on the carbonyl complexes and solution calorimetry studies of the reaction of [Rh(CO)2Cl]2 with PR2Rf (R = Ph, iPr, Cy) have been used to quantify the relative ligand donor strength for the series: PCy2Rf ≈ PiPr2Rf > PPh2Rf. The solid-state crystal structure of [Rh(CO)Cl(PPh2Rf)2] (6) is reported. Additionally, these partially fluorinated phosphine ligands (1 and 3) can be used as supporting ligation in rhodium-mediated hydrogenation reactions.
