Synthesis of Chiral Vanadium Phosphonates and Their Catalytic Activity
Ellenwood, Robert Edgar
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https://hdl.handle.net/2142/84166
Description
Title
Synthesis of Chiral Vanadium Phosphonates and Their Catalytic Activity
Author(s)
Ellenwood, Robert Edgar
Issue Date
2004
Doctoral Committee Chair(s)
Girolami, Gregory S.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Language
eng
Abstract
Treatment of vanadium starting materials with chiral and achiral phosphonic acids and phosphonates provided the soluble [BuPPh3]4[(V 2O2(OH)2)6(O3PR)8] R = CH(CH2Ph)Pr and CH(Et)Pr, [(VO)6(O3PR) 8{Cl}] R = CH2Ph, CHMePh-S, and [(V 14O22)(OH)4(O3PR)8] 6- with R = CHEtPr, CH(CH2Ph)Pr, and CH(Me)Ph- S cage complexes. These are the first reported examples of vanadium phosphonate cage molecules synthesized with racemic and enantiopure phosphonate starting materials. In addition, treatment of V2O 5 with (HO)2P(O)R in ethanol, where R = Ph and CHMePh- S, afforded (VO)(O3PR)·yEtOH·xH2O. (VO)(O3PCHMePh-S)·H2O is the first layered vanadium phosphonate material synthesized using an enantiopure phosphonic acid. These materials were tested for catalytic activity in the asymmetric epoxidation of geraniol and cinnamyl alcohol.
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