(2,4,6-Trimethylbenzoyl)diphenylphosphine Oxide Photochemistry. A Direct Time-Resolved Spectroscopic Study of Both Radical Fragments

Gregory W. Sluggett, Claudia Turro, Nicholas J. Turro, Michael W. George, Igor V. Koptyug

Research output: Journal PublicationArticlepeer-review

100 Citations (Scopus)

Abstract

The photochemistry of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (1) has been investigated using time-resolved infrared (TRIR) and time-resolved UV spectroscopy (laser flash photolysis (LFP)), in addition to conventional photochemical steady-state techniques and product analysis. Direct photolysis of 1 in dichloromethane (CH2Cl2) or n-heptane solution causes α-cleavage to afford the corresponding 2,4,6-trimethylbenzoyl (2) and diphenylphosphonyl (3) radicals. The 2,4,6-trimethylbenzoyl radical (2) is readily detected using TRIR spectroscopy, exhibiting carbonyl IR absorption maxima at 1805 and 1797 cm-1in n-heptane and CH2Cl2solution, respectively. The diphenylphosphonyl radical (3) is readily detected by LFP, exhibiting a strong UV absorption in the 300–350 nm region. Rate constants for the reactions of radicals 2 and 3 with bromotrichloromethane (BrCCl3), thiophenol (PhSH), and benzhydrol (Ph2CHOH) have been determined. Both radicals react with BrCCl3and PhSH via atom abstraction with rate constants in the 107—108M-1s-1range. Photolysis of 1 in the absence of a radical scavenger affords diphenyl[(2,4,6-trimethylbenzoyl)oxy]phosphine (9) in addition to the expected free radical-derived products. Compound 9 is also produced upon photolysis of 1 in the presence of 0.05 M BrCCl3, indicating that it is formed mainly via cage recombination of radicals 2 and 3. The reactivity of radicals 2 and 3 is discussed.

Original languageEnglish
Pages (from-to)5148-5153
Number of pages6
JournalJournal of the American Chemical Society
Volume117
Issue number18
DOIs
Publication statusPublished - May 1995
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry (all)
  • Biochemistry
  • Colloid and Surface Chemistry

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