New High Oxidation State Inorganic Complexes of Later       Transition Metals. Reaction Chemistry and Properties
{'Code': '03090005', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Jon F. Parcher', 'PO_EMAI': None, 'PO_PHON': None}
The focus of this project in the Inorganic, Bioinorganic and                    Organometallic Chemistry Program is the chemistry of high and                   unusual oxidation states of transition metals, such as                          copper(III), cobalt(IV) and cobalt(V). The project is expected                  to result in the discovery of useful and powerful new oxidizing                 agents, as well as providing biomimetic models of certain                       metalloenzymes which have recently been found to contain metals                 in high oxidation states, such as galactose oxidase, which                      contains copper(III).                                                                                                                                           Square planar cobalt(III) complexes and their anionic                           precursors will be studied and employed as precursors to highly                 oxidized organometallic species. These complexes utilize                        oxidation-resistant polyanionic chelating (PAC) ligands. Oxygen                 atom transfers catalyzed by these species will be pursued                       especially by a search for terminal cobalt(IV)-oxo complexes.                   The recently discovered copper(III) complexes which oxidize                     alcohols will be studied as biomimetic models of galactose                      oxidase and related enzymes and will also be used in a general                  exploration of the role of copper(III) complexes in oxidation                   processes.  Evidence will be sought for intermediates in the                    oxidation of phosphine to phosphine oxide by molecular oxygen                   catalyzed by osmium(VI)/(IV) systems. Ruthenium complexes of                    PAC ligands will be investigated as possible catalysts for                      alkene oxidations by molecular oxygen. "Thermodynamic ladders"                  will be developed to interrelate the formal reduction                           potentials and isomerization equilibria of diastereomeric                       complexes of the first thermodynamically stable nonplanar                       amides, and these amides will be compared to their planar                       analogues. The electrochemistry in liquid sulfur dioxide of new                 complexes of the highly protected PAC ligands will be explored                  in a search for solution stable one-electron oxidants with                      formal reduction potentials greater than 2.5 V vs. NHE.                         Attempts will be made also to extend the electrochemical                        measurements to other solvents offering a wide anodic range.
{'FirstName': 'Terrence', 'LastName': 'Collins', 'PI_MID_INIT': 'J', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Terrence J Collins', 'EmailAddress': 'tc1u@andrew.cmu.edu', 'NSF_ID': '000454694', 'StartDate': '12/01/1987', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'Carnegie-Mellon University', 'CityName': 'PITTSBURGH', 'ZipCode': '152133815', 'PhoneNumber': '4122688746', 'StreetAddress': '5000 FORBES AVE', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'Pennsylvania', 'StateCode': 'PA', 'CONGRESSDISTRICT': '12', 'CONGRESS_DISTRICT_ORG': 'PA12', 'ORG_UEI_NUM': 'U3NKNFLNQ613', 'ORG_LGL_BUS_NAME': 'CARNEGIE MELLON UNIVERSITY', 'ORG_PRNT_UEI_NUM': 'U3NKNFLNQ613'}
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{'Code': '196600', 'Text': 'SYNTHETIC INORGANIC'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1987&All=true', 'xml': '8714720.xml'}