Triazabicyclodecene:  An Effective Isotope Exchange Catalyst in CDCl<sub>3</sub>

Sabot, Cyrille; Kanduluru, Ananda Kumar; Antheaume, Cyril; Mioskowski, Charles

doi:10.1021/jo070307h

Cited by 53 publications

(43 citation statements)

References 15 publications

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“…Therefore, strong interaction between the cation and anion increases the basicity of the remote OH and NH groups of the hydrogen carbonate and prolinate anions, respectively. Although the intra‐ion pair H/D exchange cannot be entirely discarded, it more plausible that these ILs would behave as a neutral base32 during the course of all of the H/D exchange processes (Scheme ).…”

Section: Degree [%][A] Of Deuteration Of [Bmmi][x] Ils In Cdcl3 Aftermentioning

confidence: 99%

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

Zanatta¹,

Girard²,

Simon³

et al. 2014

Angew Chem Int Ed

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1-n-Butyl-2,3-dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2-Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl3 and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D2 O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses.

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Section: Degree [%][A] Of Deuteration Of [Bmmi][x] Ils In Cdcl3 Aftermentioning

confidence: 99%

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

Zanatta¹,

Girard²,

Simon³

et al. 2014

Angew Chem Int Ed

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“…Under both conditions, only traces of acetophenone were formed. By introduction of a deuterium label to the 5position of this ring (ligands [D 1 ]1a and [D 1 ]1h, Scheme 1), [26] DFT calculations allowed a further evaluation of this process: elimination of HCl from the cations 2a + , 2h + and 2i + starts by breaking of the Ru-N(pyrimidine) bond and follows a so-called roll-over metalation mechanism. Otherwise ongoing dehydrogenation of 1-phenylethanol would occur.…”

Section: Mechanistic Investigations Of the Transfer Hydrogenation In mentioning

confidence: 99%

C–H Activation at a Ruthenium(II) Complex – The Key Step for a Base‐Free Catalytic Transfer Hydrogenation?

et al. 2013

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Keywords: Transfer hydrogenation / Ruthenium / C-H activation / Mass spectrometry / Density functional calculationsRuthenium(II) complexes [(η 6 -cymene)RuCl(apypm)]BPh 4 with bidentate 2-amino-4-(2-pyridinyl)pyrimidine (apypm) ligands catalyze the transfer hydrogenation of acetophenone. Their activities are strongly dependent on the substituent pattern of the pyrimidine ring. Complexes bearing a primary amino group in the 2-position of the pyrimidine ring do not perform the catalysis in terms of a "bifunctional mechanism", although they possess protic hydrogen atoms at the amino moiety in close proximity to the metal site. Systems contain-

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“…Therefore, strong interaction between the cation and anion increases the basicity of the remote OH and NH groups of the hydrogen carbonate and prolinate anions, respectively. Although the intra-ion pair H/ D exchange cannot be entirely discarded, it more plausible that these ILs would behave as a neutral base [32] during the course of all of the H/D exchange processes (Scheme 2).…”

mentioning

confidence: 99%

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

et al. 2014

View full text Add to dashboard Cite

1-n-Butyl-2,3-dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2-Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl 3 and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D 2 O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses.

show abstract

Triazabicyclodecene: An Effective Isotope Exchange Catalyst in CDCl₃

Cited by 53 publications

References 15 publications

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

C–H Activation at a Ruthenium(II) Complex – The Key Step for a Base‐Free Catalytic Transfer Hydrogenation?

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

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Triazabicyclodecene: An Effective Isotope Exchange Catalyst in CDCl3

Cited by 53 publications

References 15 publications

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

C–H Activation at a Ruthenium(II) Complex – The Key Step for a Base‐Free Catalytic Transfer Hydrogenation?

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

Contact Info

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Triazabicyclodecene: An Effective Isotope Exchange Catalyst in CDCl₃