Oxygen-atom-abstraction of sulfenatocobalt(III) compounds mediated by methyldioxorhenium(V): A pH dependent reaction
Date
1999
Authors
Lahti, David William
Major Professor
Advisor
Espenson, James H.
Committee Member
Journal Title
Journal ISSN
Volume Title
Publisher
Abstract
A family of sulfenatocobalt compounds were reduced to thiolatocobalt(III) using the oxygen atom acceptor methyldioxorhenium(V) (MDO). MDO is formed from the reaction of methyltrioxorhenium(VII) (MTO) and hypophosphorous acid. The rate constants for the oxygen atom transfer reaction were generally evaluated using pseudo-first-order techniques with MDO in excess. The atom transfer reactions are pH dependent.
This is believed to be largely due to the basisity of the oxygen atom of the sulfenatocobalt(III) complexes. Some discrepancy was found in the data in determining the acid ionization constants (K[Subscript a]) values of the sulfenatocobalt(III) complexes. Consequently, a conjugate base species, derived from the metal complexes, may be an important reactive species. Due to the variations in the compounds, some insights and conclusions are drawn about the factors that influence reactivity of the S-0 bond with MDO.
Series Number
Journal Issue
Is Version Of
Versions
Series
Academic or Administrative Unit
Type
thesis