Experimental and computational studies on the iridium activation of aliphatic and aromatic C-H bonds of alkyl aryl ethers and related molecules

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

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Reaction of the Ir111 complex [(TpMe2)Ir(C 6H5)2(N2)] (1-N2) with ortho-cresol (2-methylphenol) occurs with cleavage of the O-H and two C(sp 3)-H bonds of the phenol and formation of the electrophilic hydride alkylidene derivative [(TpMe2)Ir(H){= C(H)C6H 4-o-O)] (2). The analogous reaction of 2-ethylphenol gives a related product 3. Both 2 and 3 have been shown to be identical to the minor, unidentified products of the already re ported reactions of 1 with anisole and phenetole, respectively. Thus, in addition to the route that leads to the known heteroatom-stabilized hydride carbene [(TpMe2)Ir(H){=C(H)OC 6H4o-}] (B), anisole can react with 1 with cleavage of the O-CH3 bond and for- mation of a new carbon-carbon bond. In contrast, only C-H bond-activation products with structures akin to B result from 1-N2 and 3,5-dimethylanisole (complex 8) or 4-fluoroanisole (9). Using anisole as a model, a computational study of the triple C-H bond activation (two aliphatic C-H bonds plus an ortho-metalation reaction) that is responsible for the formation of these heteroatom-stabilized hydride carbenes has been undertaken.

Original languageEnglish
Pages (from-to)9034-9045
Number of pages12
JournalChemistry - A European Journal
Volume15
Issue number36
DOIs
Publication statusPublished - 14 Sep 2009
Externally publishedYes

Fingerprint

Iridium
Ethers
Hydrides
Chemical activation
Hydrogen
Molecules
Carbon
Phenol
Derivatives
anisole
carbene
2-cresol

Keywords

  • C-H activation
  • Carbenes
  • Density functional calculations
  • Hydride complexes
  • Iridium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Experimental and computational studies on the iridium activation of aliphatic and aromatic C-H bonds of alkyl aryl ethers and related molecules. / Lara, Patricia; Paneque, Margarita; Poveda, Manuel L.; Santos, Laura L.; Valpuesta, José E.V.; Carmona, Ernesto; Moncho Escriva, Salvador; Ujaque, Gregori; Lledós, Agustí; Alvarez, Eleuterio; Mereiter, Kurt.

In: Chemistry - A European Journal, Vol. 15, No. 36, 14.09.2009, p. 9034-9045.

Research output: Contribution to journalArticle

Lara, P, Paneque, M, Poveda, ML, Santos, LL, Valpuesta, JEV, Carmona, E, Moncho Escriva, S, Ujaque, G, Lledós, A, Alvarez, E & Mereiter, K 2009, 'Experimental and computational studies on the iridium activation of aliphatic and aromatic C-H bonds of alkyl aryl ethers and related molecules', Chemistry - A European Journal, vol. 15, no. 36, pp. 9034-9045. https://doi.org/10.1002/chem.200900646
Lara, Patricia ; Paneque, Margarita ; Poveda, Manuel L. ; Santos, Laura L. ; Valpuesta, José E.V. ; Carmona, Ernesto ; Moncho Escriva, Salvador ; Ujaque, Gregori ; Lledós, Agustí ; Alvarez, Eleuterio ; Mereiter, Kurt. / Experimental and computational studies on the iridium activation of aliphatic and aromatic C-H bonds of alkyl aryl ethers and related molecules. In: Chemistry - A European Journal. 2009 ; Vol. 15, No. 36. pp. 9034-9045.
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AU - Poveda, Manuel L.

AU - Santos, Laura L.

AU - Valpuesta, José E.V.

AU - Carmona, Ernesto

AU - Moncho Escriva, Salvador

AU - Ujaque, Gregori

AU - Lledós, Agustí

AU - Alvarez, Eleuterio

AU - Mereiter, Kurt

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N2 - Reaction of the Ir111 complex [(TpMe2)Ir(C 6H5)2(N2)] (1-N2) with ortho-cresol (2-methylphenol) occurs with cleavage of the O-H and two C(sp 3)-H bonds of the phenol and formation of the electrophilic hydride alkylidene derivative [(TpMe2)Ir(H){= C(H)C6H 4-o-O)] (2). The analogous reaction of 2-ethylphenol gives a related product 3. Both 2 and 3 have been shown to be identical to the minor, unidentified products of the already re ported reactions of 1 with anisole and phenetole, respectively. Thus, in addition to the route that leads to the known heteroatom-stabilized hydride carbene [(TpMe2)Ir(H){=C(H)OC 6H4o-}] (B), anisole can react with 1 with cleavage of the O-CH3 bond and for- mation of a new carbon-carbon bond. In contrast, only C-H bond-activation products with structures akin to B result from 1-N2 and 3,5-dimethylanisole (complex 8) or 4-fluoroanisole (9). Using anisole as a model, a computational study of the triple C-H bond activation (two aliphatic C-H bonds plus an ortho-metalation reaction) that is responsible for the formation of these heteroatom-stabilized hydride carbenes has been undertaken.

AB - Reaction of the Ir111 complex [(TpMe2)Ir(C 6H5)2(N2)] (1-N2) with ortho-cresol (2-methylphenol) occurs with cleavage of the O-H and two C(sp 3)-H bonds of the phenol and formation of the electrophilic hydride alkylidene derivative [(TpMe2)Ir(H){= C(H)C6H 4-o-O)] (2). The analogous reaction of 2-ethylphenol gives a related product 3. Both 2 and 3 have been shown to be identical to the minor, unidentified products of the already re ported reactions of 1 with anisole and phenetole, respectively. Thus, in addition to the route that leads to the known heteroatom-stabilized hydride carbene [(TpMe2)Ir(H){=C(H)OC 6H4o-}] (B), anisole can react with 1 with cleavage of the O-CH3 bond and for- mation of a new carbon-carbon bond. In contrast, only C-H bond-activation products with structures akin to B result from 1-N2 and 3,5-dimethylanisole (complex 8) or 4-fluoroanisole (9). Using anisole as a model, a computational study of the triple C-H bond activation (two aliphatic C-H bonds plus an ortho-metalation reaction) that is responsible for the formation of these heteroatom-stabilized hydride carbenes has been undertaken.

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