Oxidation Potentials and Chemical Reactivities
{'Code': '03090003', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
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This grant in the Organic Dynamics Program provides support for                 the research of Dr. Fred Bordwell of Northwestern University.                   This work is divided into four areas: (1) the measurement of                    the acid strength of neutral and positively charged organic                     compounds, (2) the estimation of the energy required for the                    homolytic breakage of C-H, N-H and S-H bonds, (3) the effect of                 substituent groups on this latter, bond breaking process, and                   (4) organic reaction mechanisms involving the transfer of an                    electron. This work will provide insight into the pathway of                    organic reactions, especially those involving negatively                        charged species.                                                                                                                                                The ease with which a molecule H-A can be cleaved thermally                     into two radical fragments, i.e., H-A giving H atom and A atom,                 provides an important insight into its reactivity.  The                         Bordwell group has recently devised a method of estimating the                  size of such bond dissociation energies (BDE's) by combining                    the oxidation potential of the anion and the acidity constant                   of its conjugate acid, both measured in dimethyl sulfoxide                      solution.  This method will be used to estimate BDE's for a                     large number of important weak acids for which BDE's have                       hitherto been inaccessible.  By combining the oxidation                         potentials of the acid and the anion, and the acidity constant                  of the acid, the acidities of radical cations have been                         estimated.  No previous information of this type has been                       available despite the importance of radical cations as                          intermediates.  Finally, redox potentials combined with rate                    studies are expected to reveal significant new details                          concerning the role of single electron transfer in reactions of                 anions with electrophiles.
{'FirstName': 'Frederick', 'LastName': 'Bordwell', 'PI_MID_INIT': 'G', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Frederick G Bordwell', 'EmailAddress': None, 'NSF_ID': '000384102', 'StartDate': '12/15/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'Northwestern University', 'CityName': 'EVANSTON', 'ZipCode': '602080001', 'PhoneNumber': '3125037955', 'StreetAddress': '633 CLARK ST', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'Illinois', 'StateCode': 'IL', 'CONGRESSDISTRICT': '09', 'CONGRESS_DISTRICT_ORG': 'IL09', 'ORG_UEI_NUM': 'EXZVPWZBLUE8', 'ORG_LGL_BUS_NAME': 'NORTHWESTERN UNIVERSITY', 'ORG_PRNT_UEI_NUM': None}
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{'Code': '1944', 'Text': 'BIMOLECULAR PROCESSES'}
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