Electron transfer reactions of fluorotyrosyl radicals

Steven Y. Reece, Mohammad R. Seyedsayamdost, Jo Anne Stubbe, Daniel G. Nocera

Research output: Contribution to journalArticlepeer-review

48 Scopus citations


The complex Re(bpy)(CO)3CN is an excited state oxidant of tyrosine upon deprotonation of the tyrosyl phenol. A series of Re(bpy-FnY)(CO)3CN complexes ([Re]-FnY: [Re]-Y, [Re]-3-FY, [Re]-3,5-F2Y, [Re]-2,3-F2Y, [Re]-2,3,5-F3Y, [Re]-2,3,6-F3Y, and [Re]-F4Y) have been prepared so as to vary the FnY/FnY- reduction potential and thus the driving force for electron transfer in this system. Time-resolved emission and nanosecond absorption spectroscopies have been used to measure the rates for charge separation, CS, and charge recombination, CR, for each complex. A driving force analysis reveals that CS is well described by Marcus' theory for ET, is strongly driving force dependent (activated), and occurs in the normal region for ET. CR, on the other hand, is weakly driving force dependent (near activationless) and occurs in the inverted region for ET. These data demonstrate that fluorotyrosines will be powerful probes for unraveling charge transport mechanisms in enzymes that utilize tyrosyl radicals.

Original languageEnglish (US)
Pages (from-to)13654-13655
Number of pages2
JournalJournal of the American Chemical Society
Issue number42
StatePublished - Oct 25 2006
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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