B-H bond cleavage via metal-ligand cooperation by dearomatized ruthenium pincer complexes

Aviel Anaby, Burkhard Butschke, Yehoshoa Ben-David, Linda J W Shimon, Gregory Leitus, Moran Feller, David Milstein

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Organic derivatives of boronic acid are widely used reagents useful in various synthetic applications. A fundamental understanding and the exploration of new reaction pathways of boronic reagents with organometallic systems hold promise for useful advancement in chemical catalysis. Herein we present the reactions of simple boranes with dearomatized ruthenium pincer complexes based on PNP (2,6-bis(di-tert-butylphosphinomethyl)pyridine) or PNN (2-(di-tert-butylphosphinomethyl)-6-(diethylaminomethyl)pyridine) ligands. NMR studies revealed dehydrogenative addition of the borane B-H bond across the metal center and the ligand. Remarkably, new complexes were observed, which contain the boryl moiety at the benzylic carbon of the pincer ligand arm. X-ray crystal structures of new dearomatized boryl pincer complexes were obtained, and DFT calculations revealed mechanistic details of the adduct formation process through a dehydrogenative pathway. In addition, catalytic aryl-boron coupling reactions were explored. The new boryl pincer systems may possibly be useful in future postmodification techniques for ruthenium pincer complexes, as well as in catalytic B-B and B-C coupling reactions.

Original languageEnglish
Pages (from-to)3716-3726
Number of pages11
JournalOrganometallics
Volume33
Issue number14
DOIs
Publication statusPublished - Jul 28 2014

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Ruthenium
Boranes
ruthenium
cleavage
Metals
Ligands
ligands
boranes
metals
Boronic Acids
reagents
pyridines
Boron
Organometallics
Discrete Fourier transforms
Catalysis
Carbon
Crystal structure
Nuclear magnetic resonance
adducts

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Anaby, A., Butschke, B., Ben-David, Y., Shimon, L. J. W., Leitus, G., Feller, M., & Milstein, D. (2014). B-H bond cleavage via metal-ligand cooperation by dearomatized ruthenium pincer complexes. Organometallics, 33(14), 3716-3726. https://doi.org/10.1021/om500311a

B-H bond cleavage via metal-ligand cooperation by dearomatized ruthenium pincer complexes. / Anaby, Aviel; Butschke, Burkhard; Ben-David, Yehoshoa; Shimon, Linda J W; Leitus, Gregory; Feller, Moran; Milstein, David.

In: Organometallics, Vol. 33, No. 14, 28.07.2014, p. 3716-3726.

Research output: Contribution to journalArticle

Anaby, A, Butschke, B, Ben-David, Y, Shimon, LJW, Leitus, G, Feller, M & Milstein, D 2014, 'B-H bond cleavage via metal-ligand cooperation by dearomatized ruthenium pincer complexes', Organometallics, vol. 33, no. 14, pp. 3716-3726. https://doi.org/10.1021/om500311a
Anaby A, Butschke B, Ben-David Y, Shimon LJW, Leitus G, Feller M et al. B-H bond cleavage via metal-ligand cooperation by dearomatized ruthenium pincer complexes. Organometallics. 2014 Jul 28;33(14):3716-3726. https://doi.org/10.1021/om500311a
Anaby, Aviel ; Butschke, Burkhard ; Ben-David, Yehoshoa ; Shimon, Linda J W ; Leitus, Gregory ; Feller, Moran ; Milstein, David. / B-H bond cleavage via metal-ligand cooperation by dearomatized ruthenium pincer complexes. In: Organometallics. 2014 ; Vol. 33, No. 14. pp. 3716-3726.
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