2026-09-22T13:11:19Z https://www.ideals.illinois.edu/oai-pmh

oai:www.ideals.illinois.edu:2142/45620 2023-07-11 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

Hartwig, John F. Hartwig, John F. Rauchfuss, Thomas B. Girolami, Gregory S. Moore, Jeffrey S. Richers, Casseday 2013-08-22T16:55:40Z 2013-08-22T16:55:40Z 2015-08-22T10:00:26Z 2013-08 2013-08-22T16:55:40Z 2013-08 Rhodium diphosphine alkoxo alkene complexes were synthesized by the addition of unsaturated alcohols to rhodium diphosphine silylamido complexes at -78 °C. The alkoxo alkene complexes were characterized by NMR spectroscopy at 50 °C and allowed to react at either 35 °C or 70 °C. The reactions produced tetrahydrofurans and rhodium hydrido complexes by a mechanism involving alkene insertion into the rhodium alkoxo bond and β-hydrogen elimination. The reactions were monitored by 1H NMR spectroscopy, and the rate constants for insertion of the alkene ligand into the alkoxo ligand were determined by fitting the exponential curves to the data. The effects of the ancillary ligand on the rates for alkene insertion were determined by systematically varying the electronic, steric, and bite angle properties of the diphosphine ligand and observing how these changes affect the rates for alkoxo alkene complex decomposition and furan formation. The data show that the properties of the ancillary ligand do affect the rates for alkene insertion into rhodium-alkoxo bonds, and that certain characteristics or properties are desirable for promoting this reaction. Item withdrawn by Mark Zulauf (zulauf@illinois.edu) on 2013-05-21T15:04:40Z Item was in collections: University of Illinois Theses & Dissertations (ID: 1) No. of bitstreams: 1 Richers_Cass.pdf: 16461474 bytes, checksum: 75d8e3df32468fc89f8720b3865a2cd5 (MD5) Made available in DSpace on 2013-08-22T16:55:40Z (GMT). No. of bitstreams: 2 Casseday_Richers.pdf: 11214568 bytes, checksum: 0adebcd0c87896a5af3b09b0c4a24067 (MD5) license.txt: 4066 bytes, checksum: 2795fd12140619eb4bd215d464deb287 (MD5) Restriction data tranferred 2014-07-01T11:33:23-05:00 Original Data Group with Access Administrator Release Date: 2015-08-22 11:57:26 UTC Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system Item marked as restricted to the 'Administrator' Group (id=1) by Seth Robbins (srobbins@illinois.edu) on 2013-08-22T16:57:31Z Item is restricted until 2015-08-22T16:57:26Z Limited Restriction Lifted for Item 45602 on 2015-08-22T10:00:26Z. http://hdl.handle.net/2142/45620 en Copyright 2013 Casseday Richers alkenes insertions rhodium-alkoxo bonds rhodium diphosphine alkoxo alkene complexes The effects of ancillary ligand properties on the reactions of rhodium diphosphine alkoxo alkene complexes text Chemistry 1413 Chemistry 0335 University of Illinois at Urbana-Champaign Dissertation Ph.D. PHD:Chemistry -UIUC 10KS0335PHD