Synthetic, thermochemical, and catalytic studies of fluorinated tertiary phosphine ligands R{sub 2}PR{sub f} [R = Cy, Ph, {sup i}Pr; R{sub f} = CH{prime}{sub 2}CH{sub 2}(CF{sub 2}){sub 5}CF{sub 3}] in rhodium systems
The fluoroalkylphosphine compounds PR{sub 2}R{sub f} (R = Cy (1); {sup i}Pr (2); R{sub f} = CH{sub 2}CH{sub 2}(CF{sub 2}){sub 5}CF{sub 3}) have been prepared from the reactions of the Grignard reagent IMgR{sub f} and appropriate ClPR{sub 2} (R = Cy, {sup i}PR). The fluorinated phosphine ligands [PR{sub 2}R{sub f} (R = Cy) (1); {sup i}Pr (2); Ph (3); R{sub f} = CH{sub 2}CH{sub 2}(CF{sub 2}){sub 5}CF{sub 3}] react with [Rh(CO){sub 2}Cl]{sub 2} to yield the corresponding [Rh(CO)Cl(PR{sub 2}R{sub f}){sub 2}] (R = Cy) (4); {sup i}Pr (5); Ph (6) complexes. Infrared studies on the carbonyl complexes and solution calorimetry studies of the reaction of [Rh(CO){sub 2}Cl]{sub 2} with PR{sub 2}R{sub f} (R = Ph, {sup i}Pr, Cy) have been used to quantify the relative ligand donor strength for the series: PCy{sub 2}R{sub f} {approx} P{sup i}Pr{sub 2}R{sub f} {gt} PPh{sub 2}R{sub f}. The solid-state crystal structure of [Rh(CO)Cl(PPh{sub 2}R{sub f}){sub 2}] (6) is reported. Additionally, these partially fluorinated phosphine ligands (1 and 3) can be used as supporting ligation in rhodium-mediated hydrogenation reactions.
- Research Organization:
- Univ. of New Orleans, LA (US)
- DOE Contract Number:
- FG02-98ER45732
- OSTI ID:
- 20003197
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 23 Vol. 38; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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