Base-Promoted, Remote C-H Activation at a Cationic (n                         5                         -C                         5                         Me                         5                         )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C                         5                         Me                         5

Juan J. Moreno; María F. Espada; Jesús Campos; Joaquín López-Serrano; Stuart A. Macgregor; Ernesto Carmona

doi:10.1021/jacs.8b11752

Base-Promoted, Remote C-H Activation at a Cationic (n ⁵ -C ₅ Me ₅ )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C ₅ Me ₅

Juan J. Moreno, María F. Espada, Jesús Campos, Joaquín López-Serrano, Stuart A. Macgregor^*, Ernesto Carmona

^*Corresponding author for this work

School of Chemistry

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Abstract

C-H bond activation at cationic [(n ⁵ -C ₅ Me ₅ )Ir(PMe ₂ Ar′)] centers is described, where PMe ₂ Ar′ are the terphenyl phosphine ligands PMe ₂ Ar ^Xyl ₂ and PMe ₂ Ar ^Dipp ₂ . Different pathways are defined for the conversion of the five-coordinate complexes [(n ⁵ -C ₅ Me ₅ )IrCl(PMe ₂ Ar′)] ⁺ , 2(Xyl) ⁺ and 2(Dipp) ⁺ , into the corresponding pseudoallyls 3(Xyl) ⁺ and 3(Dipp) ⁺ . In the absence of an external Brønsted base, electrophilic, remote ζ C-H activation takes place, for which the participation of dicationic species, [(n ⁵ -C ₅ Me ₅ )Ir(PMe ₂ Ar′)] ²⁺ , is proposed. When NEt ₃ is present, the PMe ₂ Ar ^Dipp ₂ system is shown to proceed via 4(Dipp) ⁺ as an intermediate en route to the thermodynamic, isomeric product 3(Dipp) ⁺ . This complex interconversion involves a non-innocent C ₅ Me ₅ ligand, which participates in C-H and C-C bond formation and cleavage. Remarkably, the conversion of 4(Dipp) ⁺ to 3(Dipp) ⁺ also proceeds in the solid state.

Original language	English
Journal	Journal of the American Chemical Society
Early online date	25 Jan 2019
DOIs	https://doi.org/10.1021/jacs.8b11752
Publication status	Published - 13 Feb 2019

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Moreno, J. J., Espada, M. F., Campos, J., López-Serrano, J., Macgregor, S. A., & Carmona, E. (2019). Base-Promoted, Remote C-H Activation at a Cationic (n ⁵ -C ₅ Me ₅ )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C ₅ Me ₅. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.8b11752

Moreno, Juan J. ; Espada, María F. ; Campos, Jesús et al. / Base-Promoted, Remote C-H Activation at a Cationic (n ⁵ -C ₅ Me ₅ )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C ₅ Me ₅. In: Journal of the American Chemical Society. 2019.

@article{7bfa10e395294718b627c8b99e9e7b21,

title = "Base-Promoted, Remote C-H Activation at a Cationic (n 5 -C 5 Me 5 )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C 5 Me 5",

abstract = " C-H bond activation at cationic [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] centers is described, where PMe 2 Ar′ are the terphenyl phosphine ligands PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 . Different pathways are defined for the conversion of the five-coordinate complexes [(n 5 -C 5 Me 5 )IrCl(PMe 2 Ar′)] + , 2(Xyl) + and 2(Dipp) + , into the corresponding pseudoallyls 3(Xyl) + and 3(Dipp) + . In the absence of an external Br{\o}nsted base, electrophilic, remote ζ C-H activation takes place, for which the participation of dicationic species, [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] 2+ , is proposed. When NEt 3 is present, the PMe 2 Ar Dipp 2 system is shown to proceed via 4(Dipp) + as an intermediate en route to the thermodynamic, isomeric product 3(Dipp) + . This complex interconversion involves a non-innocent C 5 Me 5 ligand, which participates in C-H and C-C bond formation and cleavage. Remarkably, the conversion of 4(Dipp) + to 3(Dipp) + also proceeds in the solid state.",

author = "Moreno, \{Juan J.\} and Espada, \{Mar{\'i}a F.\} and Jes{\'u}s Campos and Joaqu{\'i}n L{\'o}pez-Serrano and Macgregor, \{Stuart A.\} and Ernesto Carmona",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = feb,

day = "13",

doi = "10.1021/jacs.8b11752",

language = "English",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society (ACS)",

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Moreno, JJ, Espada, MF, Campos, J, López-Serrano, J, Macgregor, SA & Carmona, E 2019, 'Base-Promoted, Remote C-H Activation at a Cationic (n ⁵ -C ₅ Me ₅ )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C ₅ Me ₅', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.8b11752

Base-Promoted, Remote C-H Activation at a Cationic (n ⁵ -C ₅ Me ₅ )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C ₅ Me ₅. / Moreno, Juan J.; Espada, María F.; Campos, Jesús et al.
In: Journal of the American Chemical Society, 13.02.2019.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Base-Promoted, Remote C-H Activation at a Cationic (n 5 -C 5 Me 5 )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C 5 Me 5

AU - Moreno, Juan J.

AU - Espada, María F.

AU - Campos, Jesús

AU - López-Serrano, Joaquín

AU - Macgregor, Stuart A.

AU - Carmona, Ernesto

PY - 2019/2/13

Y1 - 2019/2/13

N2 - C-H bond activation at cationic [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] centers is described, where PMe 2 Ar′ are the terphenyl phosphine ligands PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 . Different pathways are defined for the conversion of the five-coordinate complexes [(n 5 -C 5 Me 5 )IrCl(PMe 2 Ar′)] + , 2(Xyl) + and 2(Dipp) + , into the corresponding pseudoallyls 3(Xyl) + and 3(Dipp) + . In the absence of an external Brønsted base, electrophilic, remote ζ C-H activation takes place, for which the participation of dicationic species, [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] 2+ , is proposed. When NEt 3 is present, the PMe 2 Ar Dipp 2 system is shown to proceed via 4(Dipp) + as an intermediate en route to the thermodynamic, isomeric product 3(Dipp) + . This complex interconversion involves a non-innocent C 5 Me 5 ligand, which participates in C-H and C-C bond formation and cleavage. Remarkably, the conversion of 4(Dipp) + to 3(Dipp) + also proceeds in the solid state.

AB - C-H bond activation at cationic [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] centers is described, where PMe 2 Ar′ are the terphenyl phosphine ligands PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 . Different pathways are defined for the conversion of the five-coordinate complexes [(n 5 -C 5 Me 5 )IrCl(PMe 2 Ar′)] + , 2(Xyl) + and 2(Dipp) + , into the corresponding pseudoallyls 3(Xyl) + and 3(Dipp) + . In the absence of an external Brønsted base, electrophilic, remote ζ C-H activation takes place, for which the participation of dicationic species, [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] 2+ , is proposed. When NEt 3 is present, the PMe 2 Ar Dipp 2 system is shown to proceed via 4(Dipp) + as an intermediate en route to the thermodynamic, isomeric product 3(Dipp) + . This complex interconversion involves a non-innocent C 5 Me 5 ligand, which participates in C-H and C-C bond formation and cleavage. Remarkably, the conversion of 4(Dipp) + to 3(Dipp) + also proceeds in the solid state.

UR - https://www.scopus.com/pages/publications/85061484925

U2 - 10.1021/jacs.8b11752

DO - 10.1021/jacs.8b11752

M3 - Article

C2 - 30682245

AN - SCOPUS:85061484925

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Moreno JJ, Espada MF, Campos J, López-Serrano J, Macgregor SA, Carmona E. Base-Promoted, Remote C-H Activation at a Cationic (n ⁵ -C ₅ Me ₅ )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C ₅ Me ₅. Journal of the American Chemical Society. 2019 Feb 13. Epub 2019 Jan 25. doi: 10.1021/jacs.8b11752

Base-Promoted, Remote C-H Activation at a Cationic (n ⁵ -C ₅ Me ₅ )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C ₅ Me ₅

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