Organic Free Radical and Electron Transfer Chemistry
{'Code': '03090003', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
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This grant within the Organic Dynamics Program represents a                     continuation of the work by Martin Newcomb of Texas A&M                         University. The aim of this project is to elucidate the pathway                 of organic reactions which involve free radicals or radical                     anions. This work is quite significant in that it will                          investigate many reactions suspected to proceed by the pathway                  known as SET (single electron transfer) which have previously                   been considered to react by other mechanisms.  This will                        enhance knowledge about how organic reactions proceed, and,                     therefore, how they can be improved.                                                                                                                            Continued studies in the areas of organic free radicals and                     mechanisms of potential electron transfer processes in organic                  reactions will be investigated.  Kinetics of exceedingly fast                   carbon radical rearrangemens will be studied by the PTOC/thiol                  method developed in the Texas A&M laboratory with the objective                 of calibrating radical clocks so fast that they may be used in                  competition with diffusion-controlled second order processes in                 non-viscous solvents.  In the PTOC/thiol method,                                N-hydroxypyridine-2-thione esters are employed as  radical                      precursors and thiophenol is used as a radical trapping agent,                  and reactions with first order rate constants in excess of 1 x                  10exp-9/s at 25 degrees C can be calibrated.  Aminyl and                        aminium cation radicals from N-hydroxpyridine-2-thione                          carbamates will also be studied.  The  main objective will be                   to determine the rate constants for simple second order                         reactions (such as hydrogen atom transfer) of these                             intermediates; with basis reaction rate constants available,                    nitrogen-centered radical clocks will be calibrated.  Potential                 electron transfer processes (especially in reactions of lithium                 dialkylamides) will continue to be studied.  Verification of                    the experimentally derived oxidation potential for the                          dialklamide anion--dialkylaminyl radical couple will be sought.                  Reactions of lithium dialkylamides with trityl halides will be                 studied; recent results suggest that a previously unconsidered                  reaction process may be operating in this case.
{'FirstName': 'Martin', 'LastName': 'Newcomb', 'PI_MID_INIT': 'E', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Martin E Newcomb', 'EmailAddress': 'men@uic.edu', 'NSF_ID': '000287066', 'StartDate': '12/15/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'Texas A&M Research Foundation', 'CityName': 'COLLEGE STATION', 'ZipCode': '778454375', 'PhoneNumber': '9798626777', 'StreetAddress': '400 HARVEY MITCHELL PKWY S STE 3', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'Texas', 'StateCode': 'TX', 'CONGRESSDISTRICT': '10', 'CONGRESS_DISTRICT_ORG': 'TX10', 'ORG_UEI_NUM': 'EQH8NQ4AXFT7', 'ORG_LGL_BUS_NAME': 'TEXAS A & M RESEARCH FOUNDATION', 'ORG_PRNT_UEI_NUM': None}
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{'Code': '194400', 'Text': 'BIMOLECULAR PROCESSES'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1988&All=true', 'xml': '8816365.xml'}