Synthetic, thermochemical, and catalytic studies involving novel R{sub 2}P(OR{sub f}) [R = Alkyl or Aryl; R{sub f} = CH{sub 2}CH{sub 2}(CF{sub 2}){sub 5}CF{sub 3}] ligands
- Univ. of New Orleans, LA (United States). Dept. of Chemistry
- West Virginia Univ., Morgantown, WV (United States). Dept. of Chemistry
A series of mixed alkyl (or aryl) phosphinite compounds have been prepared from the alcohol CF{sub 3}(CF{sub 2}){sub 5}CH{sub 2}CH{sub 2}OH (R{sub f}OH) and an appropriate ClPR{sub 2} (R = OR{sub f}, Ph, {sup i}Pr, Cy) in the presence of base. A bidentate analog, (R{sub f}O){sub 2}PCH{sub 2}CH{sub 2}P(OR{sub f}){sub 2}, was synthesized in a similar manner. The ligands react with [Rh(CO){sub 2}Cl]{sub 2} yielding the complexes RhCl(CO)-(PR{sub 3}){sub 2}. The structure of RhCl(CO)(PPh{sub 2}OR{sub f}){sub 2} (6) is reported. Infrared studies of the carbonyl complexes yield a relative ligand donor strength for this series. Solution studies of the carbonyl complexes yield a relative ligand donor strength for this series. Solution calorimetry was performed on the rhodium reaction in order to quantify this donor strength scale. Both approaches lead to the same donor strength scale: PCy{sub 2}OR{sub f} > P{sup i}Pr{sub 2}OR{sub f} > PPh{sub 2}OR{sub f} > P(OR{sub f}){sub 3}. These phosphinite ligands can be used as ancillary ligation in rhodium-mediated hydrogenation. A cationic rhodium complex of the chelating ligand displays selected solubility in fluorous media and biphasic catalysis can be performed.
- Sponsoring Organization:
- National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-98ER45732
- OSTI ID:
- 315976
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 23 Vol. 17; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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