Preparation of a Silanone through Oxygen Atom Transfer to a Stable Cyclic Silylene

We report the evaporation of a stable cyclic silylene and its oxidation (with ozone or N2O) through oxygen atom transfer to form the corresponding silanone under matrix isolation conditions. As uncomplexed silanones are rare owing to their very high reactivity, this method provides an alternative ro...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2015-10, Vol.54 (42), p.12404-12409
Main Authors: Linden, Michael M., Reisenauer, Hans Peter, Gerbig, Dennis, Karni, Miriam, Schäfer, Annemarie, Müller, Thomas, Apeloig, Yitzhak, Schreiner, Peter R.
Format: Article
Language:English
Subjects:
Bonding
Computation
density functional calculations
Density functional theory
Evaporation
Insertion
IR spectroscopy
matrix isolation
Oxygen
oxygen atom transfer
Oxygen atoms
Ozone
Silanes
silicon
Spectra
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Summary:We report the evaporation of a stable cyclic silylene and its oxidation (with ozone or N2O) through oxygen atom transfer to form the corresponding silanone under matrix isolation conditions. As uncomplexed silanones are rare owing to their very high reactivity, this method provides an alternative route to these sought‐after molecules. The silanone, as well as a novel bicyclic silane with a bridgehead silicon atom derived from an intramolecular silylene CH bond insertion, were characterized by comparison of high‐resolution infrared spectra with density functional theory (DFT) computations at the M06‐2X/cc‐pVDZ level of theory. One atom at a time: Oxygen atom transfer from ozone to a stable silylene provides access to a new cyclic silanone. This bimolecular atom transfer reaction was achieved under matrix isolation conditions through co‐deposition of the silylene and ozone. Conclusive evidence for the silanone is provided by comparison of experimental and computed IR spectra, including isotopological 16O/18O replacements. Atom colors: Si=purple, C=black, O=red, H=blue.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201501844