Metalloporphyrins in Oxidative Catalysis. Oxygen Transfer Reactions of Oxochromium Porphyrins

John T. Groves, William J. Kruper

Research output: Contribution to journalArticle

22 Scopus citations

Abstract

The oxidation of chloro‐5‐10,15,20‐tetramesitylporphyrinotoiron(III) with peroxyacids affords a reactive oxoiron(IV)‐porphyrin cation radical species 2. The characterization of 2 and its oxochromium analogs 3, 4 and 5 are reviewed. The nature of reactive oxochromium species derived from chromyl reagents is also reviewed. The oxidation of triphenylphosphine by CrOTPP (11), CrOTTP (13) and CrOTMP (14) is described. Variations in the rate constants indicate that steric factors affect the rate of oxygen atom transfer. Activation parameters for the oxidation of triphenylphosphine by 14 are ΔH = 6.96 kcal/mol and ΔS = −39 eu. The oxidation of t‐butylphenylcarbinol (18) by CrOTPP gave predominantly benzaldehyde via carbon—carbon bond cleavage while the chromium(III) porphyrin‐catalyzed oxidation of 18 by iodosylbenzene afforded t‐butylphenylketone.

Original languageEnglish (US)
Pages (from-to)148-154
Number of pages7
JournalIsrael Journal of Chemistry
Volume25
Issue number2
DOIs
StatePublished - 1985
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Metalloporphyrins in Oxidative Catalysis. Oxygen Transfer Reactions of Oxochromium Porphyrins'. Together they form a unique fingerprint.

  • Cite this