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Correlation of Spectral and Electrochemical Properties of a Series of Ferrocene DerivativesCharge-transfer-to-solvent (CTTS) bands are observed in the UV/VIS spectra of a series of ferrocene derivatives (ferrocene; 1,1’-dimethyl; 1,2,3,4,5-pentamethyl; 1,2,3,4,l’,2’,3’,4’-octamethyl; and decamethyl) by the addition of increasing amounts of CCl4 to ethanol solutions. A linear correlation (slope = 8540 per cm/V) was found between the redox potential and the energy of the CTTS band, consistent with electrochemical and photochemical oxidation by removal of an electron from the same molecular orbital. Inclusion of literature data for ruthenocene and [(η^(5)-C5H5)Fe(CO)]4 results in a line with a slope of 8140 per cm/V, within 1 percent of the wavenumber to electron volt conversion factor. Calculation of association constants (K) shows a slight decrease (1.2 to 0.7 per mole fraction) as the bulkiness of the cyclopentadienyl ring increases, consistent with either a steric or a repulsive electronic effect. The extinction coefficient of the CTTS absorption was constant at approximately 1700 per Mcm .
Document ID
20160009768
Acquisition Source
Glenn Research Center
Document Type
Technical Memorandum (TM)
Authors
Aloysius F. Hepp (Glenn Research Center Cleveland, Ohio, United States)
Mark S. Wrighton (Washington University in St. Louis St Louis, Missouri, United States)
Date Acquired
August 2, 2016
Publication Date
July 1, 2016
Subject Category
Energy Production And Conversion
Inorganic, Organic And Physical Chemistry
Report/Patent Number
E-19232
GRC-E-DAA-TN31190
Paper INOR-494
Report Number: E-19232
Report Number: GRC-E-DAA-TN31190
Report Number: Paper INOR-494
Report Number: NASA/TM-2016-219106
Meeting Information
Meeting: 199th American Chemical Society National Meeting
Location: Boston, MA
Country: US
Start Date: April 22, 1990
End Date: April 27, 1990
Sponsors: American Chemical Society
Funding Number(s)
WBS: 295670.01.04.56
Distribution Limits
Public
Copyright
Public Use Permitted.
Keywords
ultraviolet spectroscopy
ferrocenes
electrochemistry
photochemical reactions

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