Identifier

etd-04132005-131235

Degree

Doctor of Philosophy (PhD)

Department

Chemistry

Document Type

Dissertation

Abstract

Attempts to study the asymmetric hydroformylation abilities of [rac-Rh2(nbd)2(et,ph-P4)](BF4)2 were made through the separation of the enantiomers of et,ph-P4 using a chiral HPLC column. Efforts were also made to optimize the NiCl2 separation chemistry for the methyl analogue of et,ph-P4 for use in asymmetric hydroformylation. A study of hydroformylation of olefins using [rac-Rh2(nbd)2(et,ph-P4)](BF4)2 in ionic liquids was also performed, leading directly to the important (and unexpected) effect of increased hydrogen pressure on [rac-Rh2(nbd)2(et,ph-P4)](BF4)2 in the acetone/water system to yield higher selectivities and rates. This has shed new light into the detrimental effect of CO on our dirhodium catalyst system. Difficulties reproducing previous initial hydroformylation rates using [rac-Rh2(nbd)2(et,ph-P4)](BF4)2 and the acetone/water solvent system led to a study of the conventions used when reporting rate data in hydroformylation, and a discussion and proposed method for reporting data that should lead to more consistent results is included here. Also included here, in an effort to help maintain synthetic continuity in the Stanley research laboratory, is an in-depth experimental methods chapter that includes detailed explanations of the synthesis and 31P spectra of all intermediates involved in the synthesis of et,ph-P4, and an explanation of collection and methods used in catalytic studies.

Date

2005

Document Availability at the Time of Submission

Release the entire work immediately for access worldwide.

Committee Chair

George Stanley

Included in

Chemistry Commons

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