Transition‐Metal‐Free Cleavage of CO

Tertiary silane 1H, 2‐[(diphenylsilyl)methyl]‐6‐methylpyridine, reacts with tris(pentafluorophenyl)borane (BCF) to form the intramolecular pyridine‐stabilized silylium 1+‐HBCF. The corresponding 2‐[(diphenylsilyl)methyl]pyridine, lacking the methyl‐group on the pyridine ring, forms classic N(py)→B a...

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Published in:Chemistry : a European journal Vol. 23; no. 55; pp. 13628 - 13632
Main Authors: Devillard, Marc, de Bruin, Bas, Siegler, Maxime A., van der Vlugt, J. I.
Format: Journal Article
Language:English
Published: WEINHEIM Wiley 04.10.2017
Wiley Subscription Services, Inc
Wiley-VCH Verlag
John Wiley and Sons Inc
Subjects:
Aromatic compounds
boron
Carbon monoxide
Chemical bonds
Chemical Sciences
Chemistry
Chemistry, Multidisciplinary
Cleavage
Communication
Communications
C−C bond formation
Deoxygenation
Ductile-brittle transition
Fracture mechanics
Physical Sciences
Pyridines
Science & Technology
silicon
small molecule activation
INSERTION
SMALL MOLECULES
FRUSTRATED LEWIS-PAIR
COMPLEXES
COORDINATION
CO
BORANE
H BOND ACTIVATION
silicon
C-C bond formation
REDUCTION
CARBON-MONOXIDE
SI-H
small molecule activation
boron
C−C bond formation
ISSN:0947-6539, 1521-3765, 1521-3765
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Summary:Tertiary silane 1H, 2‐[(diphenylsilyl)methyl]‐6‐methylpyridine, reacts with tris(pentafluorophenyl)borane (BCF) to form the intramolecular pyridine‐stabilized silylium 1+‐HBCF. The corresponding 2‐[(diphenylsilyl)methyl]pyridine, lacking the methyl‐group on the pyridine ring, forms classic N(py)→B adduct 2H‐BCF featuring an intact silane Si−H fragment. Complex 1+‐HBCF promotes cleavage of the C≡O triple bond in carbon monoxide with double C−Csp2 bond formation, leading to complex 3 featuring a B‐(diarylmethyl)‐B‐aryl‐boryloxysilane fragment. Reaction with pinacol generates bis(pentafluorophenyl)methane 4 as isolable product, proving the transition‐metal‐free deoxygenation of carbon monoxide by this main‐group system. Experimental data and DFT calculations support the existence of an equilibrium between the silylium–hydroborate ion pair and the silane–borane mixture that is responsible for the observed reactivity. Que Si, que CO: The transition‐metal‐free complete deoxygenation of CO is achieved using a combination of the tertiary silane 2‐[(diphenylsilyl)methyl]‐6‐methylpyridine (1H) and B(C6F5)3 (BCF), which generates the intramolecular pyridine‐stabilized silylium 1+‐HBCF. In the process of CO activation, one new C−H and two new C−Csp2 bonds are formed. Hydrolysis with pinacol gives H2C(C6F5)2 as isolable product. DFT has provided insight in the plausible pathway for this remarkable transformation.
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PMCID: PMC5656908
ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.201703798