Electron Apportionment in Cleavage Reactions of Radical Ions
{'Code': '03090003', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Wendy L. Richard', 'PO_EMAI': None, 'PO_PHON': None}
This grant in the Organic and Macromolecular Chemistry Program                  supports research by Dr. Przemyslaw Maslak aimed at elucidating                 the factors which control carbon-carbon bond cleavage reactions                 in a group of reaction intermediates known as ion radicals.                     Ion radicals are unique and reactive species which have complex                 and not yet well understood properties by virtue of having some                 of the characteristics of ions (electrical charge) and some of                  the characteristics of radicals (unpaired electrons) at the                     same time.  Radical ions are increasingly recognized as an                      important class of reaction intermediates as chemists learn of                  more chemical reactions shown to occur via electron transfer                    mechanisms.                                                                                                                                                     Specifically, Dr. Maslak's research is aimed at providing                       quantitative measurements of the thermodynamic and kinetic                      parameters controlling these bond cleavage reactions.  The                      investigation concentrates on the electron apportionment aspect                 of the cleavage reaction of radical ions wherein the                            odd-electron density is highly localized on one side of the                     scissile bond.  It is thought that localization of the spin                     density on the same part of the molecule throughout the                         reaction is kinetically advantageous, even if it leads to                       thermodynamically less stable products.  This research will                     explore the validity of such a spin regioconservation rule.                     The experimental distinction between the two possible ways in                   which electrons are apportioned to the fragments will be                        accomplished by linear free energy relationship studies and by                  trapping of the primary fragmentation products.  Another                        approach will use especially designed molecules in which                        electron apportionment is reflected in the regiochemistry of                    the cleavage reaction.  The influence of ion pairing and                        solvation on the fragmentation reactions will be probed by                      variation of solvent polarity and gas-phase studies.  The                       results of this work may have practical value for improving                     processes based on electron-transfer catalysis, which are                       important in synthesis, solar energy conversion, coal                           liquefaction, and other areas.
{'FirstName': 'Przemyslaw', 'LastName': 'Maslak', 'PI_MID_INIT': 'B', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Przemyslaw B Maslak', 'EmailAddress': 'nyl@psu.edu', 'NSF_ID': '000343129', 'StartDate': '07/01/1987', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'Pennsylvania State Univ University Park', 'CityName': 'UNIVERSITY PARK', 'ZipCode': '168021503', 'PhoneNumber': '8148651372', 'StreetAddress': '201 OLD MAIN', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'Pennsylvania', 'StateCode': 'PA', 'CONGRESSDISTRICT': '15', 'CONGRESS_DISTRICT_ORG': 'PA15', 'ORG_UEI_NUM': 'NPM2J7MSCF61', 'ORG_LGL_BUS_NAME': 'THE PENNSYLVANIA STATE UNIVERSITY', 'ORG_PRNT_UEI_NUM': None}
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{'Code': '1942', 'Text': 'UNIMOLECULAR PROCESSES'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1987&All=true', 'xml': '8706773.xml'}