Smooth C(alkyl)-H bond activation in rhodium complexes comprising abnormal carbene ligands

Anneke Krueger, L Jonas L Haeller, Helge Mueller-Bunz, Olha Serada, Antonia Neels, Stuart A. Macgregor, Martin Albrecht

Research output: Contribution to journalArticle

Abstract

Rhodation of trimethylene-bridged diimidazolium salts induces the intramolecular activation of an alkane-type C-H bond and yields mono-and dimetallic complexes containing a formally monoanionic C,C,C-tridentate dicarbene ligand bound to each rhodium centre. Mechanistic investigation of the C-alkyl-H bond activation revealed a significant rate enhancement when the carbene ligands are bound to the rhodium centre via C4 (instantaneous activation) as compared to C2-bound carbene homologues (activation incomplete after 2 days). The slow C-H activation in normal C2-bound carbene complexes allowed intermediates to be isolated and suggests a critical role of acetate in mediating the bond activation process. Computational modelling supported by spectroscopic analyses indicate that halide dissociation as well as formation of the agostic intermediate is substantially favoured with C4-bound carbenes. It is these processes that discriminate the C4- and C2-bound systems rather than the subsequent C-H bond activation, where the computed barriers are very similar in each case. The tridentate dicarbene ligand undergoes selective H/D exchange at the C5 position of the C4-bound carbene exclusively. A mechanism has been proposed for this process, which is based on the electronic separation of the abnormal carbene ligand into a cationic N-C-N amidinium unit and a metalla-allyl type M-C-C fragment.

Original languageEnglish
Pages (from-to)9911-9920
Number of pages10
JournalDalton Transactions
Volume40
Issue number38
DOIs
Publication statusPublished - 2011

Cite this

Krueger, A., Haeller, L. J. L., Mueller-Bunz, H., Serada, O., Neels, A., Macgregor, S. A., & Albrecht, M. (2011). Smooth C(alkyl)-H bond activation in rhodium complexes comprising abnormal carbene ligands. Dalton Transactions, 40(38), 9911-9920. https://doi.org/10.1039/c1dt11116g
Krueger, Anneke ; Haeller, L Jonas L ; Mueller-Bunz, Helge ; Serada, Olha ; Neels, Antonia ; Macgregor, Stuart A. ; Albrecht, Martin. / Smooth C(alkyl)-H bond activation in rhodium complexes comprising abnormal carbene ligands. In: Dalton Transactions. 2011 ; Vol. 40, No. 38. pp. 9911-9920.
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abstract = "Rhodation of trimethylene-bridged diimidazolium salts induces the intramolecular activation of an alkane-type C-H bond and yields mono-and dimetallic complexes containing a formally monoanionic C,C,C-tridentate dicarbene ligand bound to each rhodium centre. Mechanistic investigation of the C-alkyl-H bond activation revealed a significant rate enhancement when the carbene ligands are bound to the rhodium centre via C4 (instantaneous activation) as compared to C2-bound carbene homologues (activation incomplete after 2 days). The slow C-H activation in normal C2-bound carbene complexes allowed intermediates to be isolated and suggests a critical role of acetate in mediating the bond activation process. Computational modelling supported by spectroscopic analyses indicate that halide dissociation as well as formation of the agostic intermediate is substantially favoured with C4-bound carbenes. It is these processes that discriminate the C4- and C2-bound systems rather than the subsequent C-H bond activation, where the computed barriers are very similar in each case. The tridentate dicarbene ligand undergoes selective H/D exchange at the C5 position of the C4-bound carbene exclusively. A mechanism has been proposed for this process, which is based on the electronic separation of the abnormal carbene ligand into a cationic N-C-N amidinium unit and a metalla-allyl type M-C-C fragment.",
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Krueger, A, Haeller, LJL, Mueller-Bunz, H, Serada, O, Neels, A, Macgregor, SA & Albrecht, M 2011, 'Smooth C(alkyl)-H bond activation in rhodium complexes comprising abnormal carbene ligands', Dalton Transactions, vol. 40, no. 38, pp. 9911-9920. https://doi.org/10.1039/c1dt11116g

Smooth C(alkyl)-H bond activation in rhodium complexes comprising abnormal carbene ligands. / Krueger, Anneke; Haeller, L Jonas L; Mueller-Bunz, Helge; Serada, Olha; Neels, Antonia; Macgregor, Stuart A.; Albrecht, Martin.

In: Dalton Transactions, Vol. 40, No. 38, 2011, p. 9911-9920.

Research output: Contribution to journalArticle

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T1 - Smooth C(alkyl)-H bond activation in rhodium complexes comprising abnormal carbene ligands

AU - Krueger, Anneke

AU - Haeller, L Jonas L

AU - Mueller-Bunz, Helge

AU - Serada, Olha

AU - Neels, Antonia

AU - Macgregor, Stuart A.

AU - Albrecht, Martin

PY - 2011

Y1 - 2011

N2 - Rhodation of trimethylene-bridged diimidazolium salts induces the intramolecular activation of an alkane-type C-H bond and yields mono-and dimetallic complexes containing a formally monoanionic C,C,C-tridentate dicarbene ligand bound to each rhodium centre. Mechanistic investigation of the C-alkyl-H bond activation revealed a significant rate enhancement when the carbene ligands are bound to the rhodium centre via C4 (instantaneous activation) as compared to C2-bound carbene homologues (activation incomplete after 2 days). The slow C-H activation in normal C2-bound carbene complexes allowed intermediates to be isolated and suggests a critical role of acetate in mediating the bond activation process. Computational modelling supported by spectroscopic analyses indicate that halide dissociation as well as formation of the agostic intermediate is substantially favoured with C4-bound carbenes. It is these processes that discriminate the C4- and C2-bound systems rather than the subsequent C-H bond activation, where the computed barriers are very similar in each case. The tridentate dicarbene ligand undergoes selective H/D exchange at the C5 position of the C4-bound carbene exclusively. A mechanism has been proposed for this process, which is based on the electronic separation of the abnormal carbene ligand into a cationic N-C-N amidinium unit and a metalla-allyl type M-C-C fragment.

AB - Rhodation of trimethylene-bridged diimidazolium salts induces the intramolecular activation of an alkane-type C-H bond and yields mono-and dimetallic complexes containing a formally monoanionic C,C,C-tridentate dicarbene ligand bound to each rhodium centre. Mechanistic investigation of the C-alkyl-H bond activation revealed a significant rate enhancement when the carbene ligands are bound to the rhodium centre via C4 (instantaneous activation) as compared to C2-bound carbene homologues (activation incomplete after 2 days). The slow C-H activation in normal C2-bound carbene complexes allowed intermediates to be isolated and suggests a critical role of acetate in mediating the bond activation process. Computational modelling supported by spectroscopic analyses indicate that halide dissociation as well as formation of the agostic intermediate is substantially favoured with C4-bound carbenes. It is these processes that discriminate the C4- and C2-bound systems rather than the subsequent C-H bond activation, where the computed barriers are very similar in each case. The tridentate dicarbene ligand undergoes selective H/D exchange at the C5 position of the C4-bound carbene exclusively. A mechanism has been proposed for this process, which is based on the electronic separation of the abnormal carbene ligand into a cationic N-C-N amidinium unit and a metalla-allyl type M-C-C fragment.

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M3 - Article

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SP - 9911

EP - 9920

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

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ER -