Comparative Nucleophilic Displacement Reactions at          Phorphorus and Silicon
{'Code': '03090005', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Margaret A. Cavanaugh', 'PO_EMAI': None, 'PO_PHON': None}
In this project funded within the Inorganic, Bioinorganic and                   Organometallic Chemistry Program, Robert R. Holmes of the                       University of Massachusetts will investigate the extent to                      which phosphorus and silicon nucleophilic displacement                          reactions are described by a common basis. The study of the                     substitution reaction mechanisms of these elements relates to a                 wide range of relevant problems such as phosphoryl transfer                     reactions in biological processes and the polymerization of                     silanols and siliconates to form silicates and silicones.                                                                                                       The problem will be studied by a combined experimental and                      theoretical approach which leads to the determination of the                    energetics and stereochemistry of the likely intermediates in                   these processes. The theoretical program consists of ab-initio                  molecular orbital calculations and will treat common                            nucleophilic displacement reactions for which a series of                       entering, leaving and non-departing groups are varied. The                      experimental program involves the synthesis and structural                      characterization of five-coordinated anionic siliconates such                   as penta(alkoxy)- ,penta(hydroxy)- and pentahalo-siliconates as                 well as mixed alkylhalo-, alkoxyhydroxy- and chlorofluoro-                      penta-substituted siliconates. Single crystal X-ray structural                  analysis and solid state nuclear magnetic resonance                             measurements will be conducted to determine structural change                   between the solid and solution states and to evaluate                           activation energies for ligand exchange processes.
{'FirstName': 'Robert', 'LastName': 'Holmes', 'PI_MID_INIT': 'R', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Robert R Holmes', 'EmailAddress': 'rrh@chemistry.umass.edu', 'NSF_ID': '000297101', 'StartDate': '01/15/1989', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'University of Massachusetts Amherst', 'CityName': 'AMHERST', 'ZipCode': '010039252', 'PhoneNumber': '4135450698', 'StreetAddress': '101 COMMONWEALTH AVE', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'Massachusetts', 'StateCode': 'MA', 'CONGRESSDISTRICT': '02', 'CONGRESS_DISTRICT_ORG': 'MA02', 'ORG_UEI_NUM': 'VGJHK59NMPK9', 'ORG_LGL_BUS_NAME': 'UNIVERSITY OF MASSACHUSETTS', 'ORG_PRNT_UEI_NUM': 'VGJHK59NMPK9'}
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{'Code': '1968', 'Text': 'PHYSICAL INORGANIC'}
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