Synthesis and Reactivity of New Transition Metal Complexes  of Silicon Ligands
{'Code': '03090005', 'Directorate': {'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Margaret A. Cavanaugh'}
This project in the Inorganic, Bioinorganic, and Organometallic                 Program is in the area of organosilicon chemistry.  In addition                 to advancing knowledge of metal-mediated reactions of                           organosilicon compounds, the results of the project are                         expected to be useful in the synthesis of new                                   silicon-containing advanced materials.                                                                                                                          New classes of transition metal complexes of organosilicon                      ligands will be synthesized by a variety of methods,                            emphasizing compounds which will serve as models of postulated                  catalytic intermediates, or which should exhibit new reaction                   chemistry.  New synthetic routes to silicon-substituted                         metal-silyls and -disilyls will be developed which employ                       silylene transfer reactions from hexamethysilacyclopropane,                     cyclo-Si6Me12, and cyclo-Si3R6.  Synthetic transformations                      involving metal-initiated silylene transfer as well as free                     silylenes will be explored.  The conversion of substituted                      silyls and disilyls to silene, disilene, and metallacyclic                      complexes will then be studied.  Structural and spectroscopic                   techniques will be used to determine the extent of pi-bonding                   in the silaolefin complexes.  Insertion and ring-expansion                      reactions of silene and disilene complexes will be examined,                    and the photolytic dissociation of free silaolefins from the                    complexes will be attempted.  Silylidene or silylenoid                          intermediates, generated from substituted silyls or free                        silylenes, will be trapped as silametallacycles with olefins                    and alkynes. Finally, mechanistic studies of silylene insertion                 reactions will focus on (1) silylene extrusion (independent                     of metal substrates), (2) the role of Lewis bases on silylene                   generation and reactivity, (3) the interactions of                              dimethylsilylene with metal substrates.
{'FirstName': 'Donald', 'LastName': 'Berry', 'EmailAddress': 'dberry@sas.upenn.edu', 'StartDate': '08/15/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'University of Pennsylvania', 'CityName': 'Philadelphia', 'ZipCode': '191046205', 'PhoneNumber': '2158987293', 'StreetAddress': 'Research Services', 'CountryName': 'United States', 'StateName': 'Pennsylvania', 'StateCode': 'PA'}
{'Code': '1968', 'Text': 'PHYSICAL INORGANIC'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1988&All=true', 'xml': '8808161.xml'}