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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Vydané v:	Chemistry : a European journal Ročník 23; číslo 55; s. 13628 - 13632
Hlavní autori:	Devillard, Marc, de Bruin, Bas, Siegler, Maxime A., van der Vlugt, J. I.
Médium:	Journal Article
Jazyk:	English
Vydavateľské údaje:	WEINHEIM Wiley 04.10.2017 Wiley Subscription Services, Inc Wiley-VCH Verlag John Wiley and Sons Inc
Predmet:	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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Popis
Shrnutí:	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.
Bibliografia:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23 PMCID: PMC5656908
ISSN:	0947-6539 1521-3765 1521-3765
DOI:	10.1002/chem.201703798