Unsaturated Hydrocarbon Cation Radical Chemistry
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This grant in Organic and Macromolecular Chemistry provides                     support for the research of Professor Stephen Nelsen,                           University of Wisconsin, whose work focuses on the chemistry of                 organic radical cations.  Such species are thought to be                        important intermediates in a number of oxidation processes. A                   full understanding of oxidation processes has important                         practical implications in controlling a variety of oxidations,                  particularly ones that are destructive to organic molecules.                                                                                                    Changes in nuclear and electronic structure upon electron                       removal from unsaturated hydrocarbon derivatives will be probed                 by optical and ESR spectroscopy, PE spectroscopy and cyclic                     voltammetry.  Energy differences in the gas phase and in                        solution between the neutral and ionic state will be                            determined. Semiempirical calculations will also be carried                     out.  A series of sesquibicyclic alkenes, which will change the                 amount of pyramidalization which occurs upon electron loss,                     will be prepared.  Comparison of compounds with C=C+. as the                    formal charge-bearing center with other compounds having the                    same alkyl groups but NN+. bearing the charge will reveal                       differences in sigma, pi interactions.  Chemistry initiated by                  irradiation into the sigma, pi transition of these compounds                    will also be surveyed.  Studies of CO bond formation upon chain                 reaction of dioxygen with these compounds (initiated by their                   cation radicals) will continue.  Unusual selectivities result                   from the peroxyl-carbocation and peroxide cation radical                        intermediates, and four, five, and six-membered ring peroxides                  (dioxetanes, dioxolanes, and endoperoxides), many of which are                  not available by other methods, have been shown to be formed.                   Extensions of this Cation Radical Chain Catalyzed (CRCC)                        chemistry to additions of carbon monoxide, isonitriles, nitrous                 oxide, and acetylenes will be explored.
{'FirstName': 'Stephen', 'LastName': 'Nelsen', 'PI_MID_INIT': 'F', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Stephen F Nelsen', 'EmailAddress': 'nelsen@chem.wisc.edu', 'NSF_ID': '000302388', 'StartDate': '05/01/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'University of Wisconsin-Madison', 'CityName': 'MADISON', 'ZipCode': '537151218', 'PhoneNumber': '6082623822', 'StreetAddress': '21 North Park Street', 'StreetAddress2': 'Suite 6301', 'CountryName': 'United States', 'StateName': 'Wisconsin', 'StateCode': 'WI', 'CONGRESSDISTRICT': '02', 'CONGRESS_DISTRICT_ORG': 'WI02', 'ORG_DUNS_NUM': '161202122', 'ORG_LGL_BUS_NAME': 'UNIVERSITY OF WISCONSIN SYSTEM', 'ORG_PRNT_DUNS_NUM': '041188822'}
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{'Code': '1942', 'Text': 'UNIMOLECULAR PROCESSES'}
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