Reversible Concerted Metalation-Deprotonation C-H Bond Activation by [CpRhCl2](2)

The reversibility of the concerted metalation-deprotonation exchange of eight para-substituted phenyl-pyridines is examined with the parent Cp*RhCl(kappa-C,N-NC5H4-C6H4). Equilibrium constants are determined, and the free energies are used to extract the most important parameters that control the th...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 84; no. 20; pp. 12960 - 12965
Main Authors VanderWeide, Andrew I., Brennessel, William W., Jones, William D.
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 18.10.2019
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
CYCLOMETALATION
ORTHO-PALLADATION
MECHANISM
RH
KINETICS
IMINES
ASTERISK-IR
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Summary:The reversibility of the concerted metalation-deprotonation exchange of eight para-substituted phenyl-pyridines is examined with the parent Cp*RhCl(kappa-C,N-NC5H4-C6H4). Equilibrium constants are determined, and the free energies are used to extract the most important parameters that control the thermodynamics. K-eq values are found to correlate best with heterolytic C-H bond strengths but in a way that is not obvious considering the electrophilic nature of these activations.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.9b01716