The Chemistry of Organosamarium(II) and Related Complexes
{'Code': '03090005', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Raymond Mackay', 'PO_EMAI': None, 'PO_PHON': None}
This project in the Inorganic, Bioinorganic and Organometallic                  Chemistry Program deals with the organometallic chemistry of                    the lanthanide metals, especially samarium. Organosamarium                      complexes have been shown by the Principal Investigator to be                   unusually powerful reducing agents which have the advantage of                  being soluble in a number of common organic solvents, in which                  they effect a variety of highly unusual transformations of                      organic molecules. Further studies of these complexes are                       expected both to define better their utility as synthetic                       reagents and to provide an understanding of their chemical                      reactivity.                                                                                                                                                     The objective of this project is to determine the factors which                 control the special reactivity of organolanthanide(II)                          complexes, especially of organosamarium(II) complexes. Of                       special interest is a series of related Sm(II)-mediated                         reactions in which carbon-carbon double or triple bonds, or                     nitrogen-nitrogen double bonds, are activated and reacted with                  CO to give significantly transformed products. These will                       provide excellent opportunities to probe the principles of                      Sm(II) reactivity and therefore will be studied in detail. This                 chemistry will be extended to C-C bond cleavage reactions and                   the use of Sm(II)-generated dihaptoacyl complexes to effect                     cyclization of straight-chain alkyls. The effect of the Lewis                   acid center on Sm(II) reactions will be examined by studying                    reductive transformations using an external reductant in the                    presence of bis(pentamethylcyclopentadiene)-                                    bis(THF)samarium(III) and bis(pentamethylcyclopentadiene)-                      (THF)europium(II). The results of these experiments, together                   with studies of methods for effecting reductive Sm-O bond                       cleavage, are expected to lead to reductive transformation                      systems which are catalytic in samarium. The synthesis of                       reactive bridged bimetallic Sm(II) reagents will be explored                    also, as will the chemical consequences of the unusual bent                     structure of the bis(pentamethylcyclopentadiene)samarium(II) in                 the activation of alkenes by this reagent.
{'FirstName': 'William', 'LastName': 'Evans', 'PI_MID_INIT': 'J', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'William J Evans', 'EmailAddress': 'wevans@uci.edu', 'NSF_ID': '000333652', 'StartDate': '02/01/1989', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'University of California-Irvine', 'CityName': 'IRVINE', 'ZipCode': '926970001', 'PhoneNumber': '9498247295', 'StreetAddress': '160 ALDRICH HALL', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'California', 'StateCode': 'CA', 'CONGRESSDISTRICT': '47', 'CONGRESS_DISTRICT_ORG': 'CA47', 'ORG_UEI_NUM': 'MJC5FCYQTPE6', 'ORG_LGL_BUS_NAME': 'UNIVERSITY OF CALIFORNIA IRVINE', 'ORG_PRNT_UEI_NUM': 'MJC5FCYQTPE6'}
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{'Code': '196600', 'Text': 'SYNTHETIC INORGANIC'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1988&All=true', 'xml': '8822093.xml'}