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Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds.

ABSTRACT: B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds induce C-H activation of acetone to yield a (2-propenyloxy)aminoborane and an unsymmetrical 1-(2-propenyloxy)-2-hydrodiborene, respectively. DFT calculations showed that, despite their stark electronic differences, both the B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds activate acetone via a similar coordination-deprotonation mechanism. In contrast, the reaction of acetone with a cAAC-supported diboracumulene yielded a unique 1,2,3-oxadiborole, which according to DFT calculations also proceeds via an unsymmetrical diborene, followed by intramolecular hydride migration and a second C-H activation of the enolate ligand.

SUBMITTER: Bohnke J

PROVIDER: S-EPMC6009441 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds.

Böhnke Julian J Brückner Tobias T Hermann Alexander A González-Belman Oscar F OF Arrowsmith Merle M Jiménez-Halla J Oscar C JOC Braunschweig Holger H

Chemical science 20180430 24

B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds induce C-H activation of acetone to yield a (2-propenyloxy)aminoborane and an unsymmetrical 1-(2-propenyloxy)-2-hydrodiborene, respectively. DFT calculations showed that, despite their stark electronic differences, both the B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds activate acetone <i>via</i> a similar coordination-deprotonation mechanism. In contrast, the reaction of a ...[more]

PMID: 30009006

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Project description:In a natural environment, Fe(ii) adsorbed onto the surfaces of natural particles to form various surface complex species can influence the transformation of contaminants. The reductive reactivity of the [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples are close correlated with the surrounding conditions. In this study, we investigated the effects of Si(iv) on the reductive reactivity of [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples adsorbed onto γ-Al2O3. Experiments were conducted under different conditions to investigate the effects of Si(iv) on the reactivity of [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples for 2-nitrophenol (2-NP, selected as the model pollutant) reduction in γ-Al2O3 suspensions. Kinetics results revealed that chemical adsorption is the rate limiting step in Fe(ii) and Si(iv) adsorption processes and the reduction of 2-NP is an endothermic reaction. The linear correlations between the reduced peak oxidation potential (E p) (versus SCE) and 2-NP reduction rate (ln k), and between the adsorbed Fe(ii) density (ρ Fe(II)) and ln k, illustrated that E p and ρ Fe(II) are two key factors in the inhibiting effects of Si(iv) on the reductive reactivity of Fe(iii)/Fe(ii) couples on γ-Al2O3. The results of Fe K-edge X-ray absorption spectroscopy revealed that the increase of Si(iv) concentration resulted in the gradual change in the composition of the adsorbed Fe species from pure [triple bond, length as m-dash]AlOFe+ (γ-Al2O3 surface-bound Fe(ii) species with higher reductive reactivity) to a mixture of [triple bond, length as m-dash]AlOFe+ and [triple bond, length as m-dash]SiOFe+ (SiO2 surface-bound Fe(ii) species with lower reductive reactivity), leading to the decrease in ρ Fe(II), the positive shift in E p, the increase in activation energy (E a), and consequently the decrease in the reduction rate (ln k) of 2-NP.

Dataset Information

Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds.

Publications

Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds.

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