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Transition‐Metal‐Free Cleavage of CO
Author(s) -
Devillard Marc,
de Bruin Bas,
Siegler Maxime A.,
van der Vlugt J. I.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703798
Subject(s) - chemistry , borane , pyridine , intramolecular force , silane , medicinal chemistry , carbon monoxide , bond cleavage , adduct , transition metal , aryl , triple bond , reactivity (psychology) , deoxygenation , photochemistry , double bond , stereochemistry , polymer chemistry , organic chemistry , catalysis , medicine , alkyl , alternative medicine , pathology
Tertiary silane 1 H , 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 2 H ‐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−C sp2 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.