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Synthetic, Thermochemical, and Catalytic Studies of Fluorinated Tertiary Phosphine Ligands R 2 PR f [R = Cy, Ph, i Pr; R f = CH‘ 2 CH 2 (CF 2 ) 5 CF 3 ] in Rhodium Systems

1999; American Chemical Society; Volume: 38; Issue: 23 Linguagem: Inglês

10.1021/ic990430u

1520-510X

Dale Smith, Edwin D. Stevens, Steven P. Nolan,

Organometallic Complex Synthesis and Catalysis

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.