Reaction of aryl iodides with (PCP)Pd(II)-alkyl and aryl complexes: Mechanistic aspects of carbon-carbon bond formation

Heinz Bernhard Kraatz, Milko van der Boom, Yehoshoa Ben-David, David Milstein

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Abstract

The reaction of the PCP-type complex Pd(Me) {2,6-(1Pr2PCH2)2C6H 3} (3) with phenyl iodide results in the formation of Pd(1) {2,6-(1Pr2PCH2)2C6H 3} (5). methyl iodide, toluene, and biphenyl. Formation of Pd(Ph) {2,6-(1Pr2PCH2)2C6H 3} (4) is observed during the reaction by 31P NMR. Reaction of 4 with aryl iodides results in the formation of 5 and Ph-Ph. Ph-Ar, and Ar-Ar, products indicative of a radical reaction. Under pseudo-first-order conditions, the rates of the reactions follow the order p-OMe > p-Me > H > p-NO2 > m-Cl. The reaction is likely to involve electron transfer from 4 to the aryl iodide followed by fast decomposition of a postulated radical cation [Pd(Ph) {2,6-(1Pr2PCH2)2C6H 3}]+. (4+.) to give a phenyl radical and [Pd {2,6-(1Pr2PCH2)2C6H 3}]+ (6+). Facile decomposition of the aryl iodide radical union generates an aryl radical and I . Recombination of aryl radicals gives rise to mixed biaryls, and 6+ combines with 1 to give 5.

Original languageEnglish
Pages (from-to)163-171
Number of pages9
JournalIsrael Journal of Chemistry
Volume41
Issue number3
Publication statusPublished - 2001

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Iodides
Carbon
Decomposition
Toluene
Cations
Nuclear magnetic resonance
Electrons

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Reaction of aryl iodides with (PCP)Pd(II)-alkyl and aryl complexes : Mechanistic aspects of carbon-carbon bond formation. / Kraatz, Heinz Bernhard; van der Boom, Milko; Ben-David, Yehoshoa; Milstein, David.

In: Israel Journal of Chemistry, Vol. 41, No. 3, 2001, p. 163-171.

Research output: Contribution to journalArticle

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AB - The reaction of the PCP-type complex Pd(Me) {2,6-(1Pr2PCH2)2C6H 3} (3) with phenyl iodide results in the formation of Pd(1) {2,6-(1Pr2PCH2)2C6H 3} (5). methyl iodide, toluene, and biphenyl. Formation of Pd(Ph) {2,6-(1Pr2PCH2)2C6H 3} (4) is observed during the reaction by 31P NMR. Reaction of 4 with aryl iodides results in the formation of 5 and Ph-Ph. Ph-Ar, and Ar-Ar, products indicative of a radical reaction. Under pseudo-first-order conditions, the rates of the reactions follow the order p-OMe > p-Me > H > p-NO2 > m-Cl. The reaction is likely to involve electron transfer from 4 to the aryl iodide followed by fast decomposition of a postulated radical cation [Pd(Ph) {2,6-(1Pr2PCH2)2C6H 3}]+. (4+.) to give a phenyl radical and [Pd {2,6-(1Pr2PCH2)2C6H 3}]+ (6+). Facile decomposition of the aryl iodide radical union generates an aryl radical and I . Recombination of aryl radicals gives rise to mixed biaryls, and 6+ combines with 1 to give 5.

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