Title

An Uncanny Dehydrogenation Mechanism: Polar Bond Control over Stepwise or Concerted Transition States

Document Type

Article

Publication Date

2017

Abstract

The mechanism of N-heterocycle dehydrogenation with the bifunctional (iPrPNP)Fe(CO)(H) catalyst was investigated. N-Heterocyclic substrates are completely dehydrogenated with barriers of the C−N dehydrogenation (ΔG‡ = 9.6−22.2 kcal/mol) significantly lower than barriers of the C−C dehdyrogenation (ΔG‡ = 37.4−42.2 kcal/mol). Therefore, dehydrogenation only occurs at the C−N bond. Interestingly, substrates with polarized C−N bonds entail stepwise (proton then hydride) dehydrogenation, and substrates with relatively unpolarized C−N bonds are dehydrogenated through a concerted proton/hydride transfer TS.

DOI

10.1021/acs.inorgchem.6b01800

Comments

Bellows, S. M.; Chakraborty, S.; Gary, J . B.; Jones, W. D.: Cundari. T. R. "An uncanny dehydrogenation mechanism: polar bond control over stepwise or concerted transition states" Organometallics. 2017, 56, 5519-5524.

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