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Physical Sciences and Mathematics Commons

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Chemistry

Oxidation

2011

Trinity University

Articles 1 - 2 of 2

Full-Text Articles in Physical Sciences and Mathematics

Dications Of Benzylidenefluorene And Diphenylmethylidene Fluorene: The Relationship Between Magnetic And Energetic Measures Of Antiaromaticity, Catherine Do, Julianne Hatfield, Shirali Patel, D Vasudevan, Cornelia Tirla, Nancy S. Mills Jan 2011

Dications Of Benzylidenefluorene And Diphenylmethylidene Fluorene: The Relationship Between Magnetic And Energetic Measures Of Antiaromaticity, Catherine Do, Julianne Hatfield, Shirali Patel, D Vasudevan, Cornelia Tirla, Nancy S. Mills

Chemistry Faculty Research

Oxidation of m- and p-substituted benzylidene fluorenes to antiaromatic dications was attempted by electrochemical and chemical means. Electrochemical oxidation to dications was successful for benzylidene fluorenes with p-methoxy, p-methyl, p-fluoro, and unsubstituted phenyl rings in the 3-position; attempts to oxidize the m-substituted derivatives via electrochemistry were unsuccessful. Chemical oxidation with SbF5/SO2ClF gave the dication of 9-[(4-methoxyphenyl)methylene]-9H-fluorene cleanly; oxidation of all other substituted benzylidene fluorenes resulted in mixtures of products. The excellent linear relationship between the chemical shifts calculated by the GIAO method and the experimental shifts for the p-methoxy-substituted benzylidene fluorene dication …


Antiaromatic Dianions: Dianions Of Dixanthylidene By Reduction And Attempted Excited-State Deprotonation, Mary Black, Clifford Woodford, Nancy S. Mills Jan 2011

Antiaromatic Dianions: Dianions Of Dixanthylidene By Reduction And Attempted Excited-State Deprotonation, Mary Black, Clifford Woodford, Nancy S. Mills

Chemistry Faculty Research

Reduction of dixanthylidene with potassium or lithium resulted in formation of the antiaromatic dianion in high yield. Attempts to form the dianion by excited-state deprotonation of dixanthene with n-butyllithium/TMEDA resulted in formation of the tetraanion from deprotonation ortho to the oxygen. Orientation of the sp3 hydrogens presumably allows preferential deprotonation of the xanthene rings.