Transition‐Metal‐Free Cleavage of CO

نویسندگان

  • Marc Devillard
  • Bas de Bruin
  • Maxime A Siegler
  • J I van der Vlugt
چکیده

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.

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عنوان ژورنال:

دوره 23  شماره 

صفحات  -

تاریخ انتشار 2017