Mechanisms of Bond-Making and Bond-Breaking; Role of RadicalIons (Chemistry)
{'Code': '03090003', 'Directorate': {'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Wendy L. Richard'}
This grant in the Organic and Macromolecular Chemistry Program                  supports reserach by Prof. Frederick Greene, which is centered                  around the elucidation of reaction mechanisms.  Reaction                        mechanisms are the detailed sequences of bond-making and bond-                  breaking which constitute chemical change; understanding these                  processes and their controlling factors is a critical element                   in controlling chemical reactivity.  Dr. Greene's research will                 focus on the mechanisms of bond formation and rupture by both                   catalytic and non-catalytic means.  This work will pursue a                     relatively new way of initiating organic reactions by "electron                 catalysis," that is: the addition or removal of an electron                     from a reactant to form a highly reactive radical ion.                                                                                                          Although much is known about the groups of reactive                             intermediates known as radicals (unpaired electrons) and ions                   (electrically charged), much less is currently known about the                  chemistry of radical ions, which are odd-electron species also                  carrying charge.  A major objective of the Greene group is to                   obtain new information on the chemical properties of radical                    ions.  An exploratory study is planned to examine the role of                   radical ions in selected addition, cycloaddition, retrocyclo-                   addition, and rearrangement reactions.  Various electron donors                 and acceptors will be evaluated, with attention to                              electrochemical information and to some consideration of new                    donors.  Retrocycloaddition reactions of four-membered ring                     cyclic azo compounds (diazetines) constitute an important test                  case for mechanisms of bond-breaking processes.  Recent results                 have provided promising routes for syntheses of substances                      needed.  Experiments are also planned to probe the mechanism of                 retrocycloaddition of diazetines initiated by electron                          acceptors.
{'FirstName': 'Frederick', 'LastName': 'Greene', 'EmailAddress': None, 'StartDate': '06/01/1987', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'Massachusetts Institute of Technology', 'CityName': 'Cambridge', 'ZipCode': '021394301', 'PhoneNumber': '6172531000', 'StreetAddress': '77 MASSACHUSETTS AVE', 'CountryName': 'United States', 'StateName': 'Massachusetts', 'StateCode': 'MA'}
{'Code': '1942', 'Text': 'UNIMOLECULAR PROCESSES'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1987&All=true', 'xml': '8711478.xml'}