Synthetic, mechanistic, and theoretical studies on the generation of iridium hydride alkylidene and iridium hydride alkene isomers

Patricia Lara, Margarita Paneque, Manuel L. Poveda, Laura L. Santos, José E.V. Valpuesta, Verónica Salazar, Ernesto Carmona, Salvador Moncho Escriva, Gregori Ujaque, Agustí Lledós, Celia Maya, Kurt Mereiter

Research output: Contribution to journalArticle

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Abstract

Experimental and theoretical studies on equilibria between iridium hydride alkylidene structures, [(TpMe2)Ir(H){=C(CH2R)ArO}] (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate; R = H, Me; Ar = substituted C6H4 group), and their corresponding hydride olefin isomers, [(TpMe2)Ir(H){R(H)C=C(H)OAr}], have been carried out. Compounds of these types are obtained either by reaction of the unsaturated fragment [(TpMs2)Ir(C6H5)2] with o-C6H4(OH)CH2R, or with the substituted anisoles 2,6-Me2C6H3OMe, 2,4,6Me 3C6H2OMe, and 4-Br-2,6-Me2C 6H2OMe. The reactions with the substituted anisoles require not only multiple C-H bond activation but also cleavage of the Me-OAr bond and the reversible formation of a C-C bond (as revealed by 13C labeling studies). Equilibria between the two tautomeric structures of these complexes were achieved by prolonged heating at temperatures between 100 and 140°C, with interconversion of isomeric complexes requiring inversion of the metal configuration, as well as the expected migratory insertion and hydrogen-elimination reactions. This proposal is supported by a detailed computational exploration of the mechanism at the quantum mechanics (QM) level in the real system. For all compounds investigated, the equilibria favor the alkylidene structure over the olefinic isomer by a factor of between approximately 1 and 25. Calculations demonstrate that the main reason for this preference is the strong Ir-carbene interactions in the carbene isomers, rather than steric destabilization of the olefinic tautomers.

Original languageEnglish
Pages (from-to)9046-9057
Number of pages12
JournalChemistry - A European Journal
Volume15
Issue number36
DOIs
Publication statusPublished - 14 Sep 2009
Externally publishedYes

Fingerprint

Anisoles
Iridium
Alkenes
Hydrides
Isomers
Theoretical Models
Borates
Mechanics
Heating
Hydrogen
Quantum theory
Metals
Labeling
Temperature
Chemical activation
carbene

Keywords

  • Alkenes
  • C-H activation
  • Carbenes
  • Density functional calculations
  • Iridium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Lara, P., Paneque, M., Poveda, M. L., Santos, L. L., Valpuesta, J. E. V., Salazar, V., ... Mereiter, K. (2009). Synthetic, mechanistic, and theoretical studies on the generation of iridium hydride alkylidene and iridium hydride alkene isomers. Chemistry - A European Journal, 15(36), 9046-9057. https://doi.org/10.1002/chem.200900654

Synthetic, mechanistic, and theoretical studies on the generation of iridium hydride alkylidene and iridium hydride alkene isomers. / Lara, Patricia; Paneque, Margarita; Poveda, Manuel L.; Santos, Laura L.; Valpuesta, José E.V.; Salazar, Verónica; Carmona, Ernesto; Moncho Escriva, Salvador; Ujaque, Gregori; Lledós, Agustí; Maya, Celia; Mereiter, Kurt.

In: Chemistry - A European Journal, Vol. 15, No. 36, 14.09.2009, p. 9046-9057.

Research output: Contribution to journalArticle

Lara, P, Paneque, M, Poveda, ML, Santos, LL, Valpuesta, JEV, Salazar, V, Carmona, E, Moncho Escriva, S, Ujaque, G, Lledós, A, Maya, C & Mereiter, K 2009, 'Synthetic, mechanistic, and theoretical studies on the generation of iridium hydride alkylidene and iridium hydride alkene isomers', Chemistry - A European Journal, vol. 15, no. 36, pp. 9046-9057. https://doi.org/10.1002/chem.200900654
Lara, Patricia ; Paneque, Margarita ; Poveda, Manuel L. ; Santos, Laura L. ; Valpuesta, José E.V. ; Salazar, Verónica ; Carmona, Ernesto ; Moncho Escriva, Salvador ; Ujaque, Gregori ; Lledós, Agustí ; Maya, Celia ; Mereiter, Kurt. / Synthetic, mechanistic, and theoretical studies on the generation of iridium hydride alkylidene and iridium hydride alkene isomers. In: Chemistry - A European Journal. 2009 ; Vol. 15, No. 36. pp. 9046-9057.
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AU - Valpuesta, José E.V.

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AU - Carmona, Ernesto

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