Photocatalytic oxidation of bromide to bromine

Kelvin Yun Da Tsai, I. Jy Chang

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Three consecutive bimolecular reactions are employed to photocatalyze bromide oxidation to bromine. The system consists of a ruthenium(II) complex, [Ru(deeb)2(dmbpy)]2+ (deeb = 4,4'-diethylester-2,2'-bipyridine; dmbpy = 4,4'-dimethyl-2,2'-bipyridine), 4-bromobenzenediazonium tetrafluoroborate (ArN2BF4), and Br-. Varying reagent concentrations allowed us to optimize the sequence of reactions for product formation. The electronically excited ruthenium complex (Ru) reacts first with ArN2BF4 to produce a ruthenium(III) (RuIII) intermediate, triggering a subsequent reaction with Br-. Transient absorption measured at 486 and 380 nm provides insight into the time-dependent concentrations of Ru, RuIII, and Br2•- Without interference of backelectron transfer, the rate constant for an equal concentration bimolecular reaction of Br2•- was determined to be 5 × 109 M-1 s-1. The final products, bromine and tribromide, were spectroscopically characterized, and the turnover number (TON) was 230.

Original languageEnglish
Pages (from-to)693-696
Number of pages4
JournalInorganic Chemistry
Volume56
Issue number2
DOIs
Publication statusPublished - 2017 Jan 17

    Fingerprint

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this