1. Electrochemical properties of diphosphonate-bridged palladacycles and their reactivity in arene phosphonation
- Author
-
Yulia B. Dudkina, Tatyana Gryaznova, Oleg G. Sinyashin, Olga N. Kataeva, Yulia H. Budnikova, and Mikhail Khrizanforov
- Subjects
Quinoline ,Nuclear magnetic resonance spectroscopy ,Condensed Matter Physics ,Photochemistry ,Medicinal chemistry ,Redox ,Catalysis ,Carbon paste electrode ,chemistry.chemical_compound ,chemistry ,Electrochemistry ,General Materials Science ,Reactivity (chemistry) ,Electrical and Electronic Engineering ,Cyclic voltammetry ,Acetonitrile - Abstract
A series of diphosphonate-bridged dipalladacycles [(phpy)Pd(EtO)2P(O)]2, [(bhq)Pd(EtO)2P(O)]2, [(phpz)Pd(EtO)2P(O)]2 (phpy=2-phenylpyridine, bhq=benzo[h]quinoline, phpz=1-phenylpyrazole), which are known to be involved in catalytic CāH phosphonation reactions, was prepared and characterized by NMR spectroscopy and cyclic voltammetry in acetonitrile solutions and in carbon paste electrode. Diphosphonate dipalladacycles are oxidized irreversibly at more positive potentials as distinguished from related acetate palladacycles. Electrochemical preparative oxidations carried out under mild conditions without any specially added oxidants quantitatively afforded corresponding arylphosphonates. For complete conversion of dipalladacycles into arylphosphonates, four electrons per each palladium atom are required, that probably indicates a mechanism involving Pd(IV)/Pd(II) redox couple.
- Published
- 2015
- Full Text
- View/download PDF