Exploring the Reactivity of a Frustrated Sn/P Lewis Pair: The Highly Selective Complexation of the cis‐Azobenzene Photoisomer

The reactivity of the geminal frustrated Lewis pair (FLP) (F5C2)3SnCH2P(tBu)2 (1) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H3CC(O)CH=CH2, Ph[C(O)]2Ph, PhN=NPh and Me3SiCHN2), featuring polar or non‐polar multiple bonds and/or represent α,β‐unsaturat...

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Bibliographic Details
Published in:Chemistry : a European journal 2021-02, Vol.27 (11), p.3793-3798
Main Authors: Holtkamp, Philipp, Poier, Dario, Neumann, Beate, Stammler, Hans‐Georg, Mitzel, Norbert W.
Format: Article
Language:English
Subjects:
activation
Adducts
Azo compounds
Benzil
Chemistry
Complexation
fluoroalkyl groups
frustrated Lewis pairs
Magnetic resonance spectroscopy
NMR
NMR spectroscopy
Nuclear magnetic resonance
small molecules
Stereoselectivity
tin
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Summary:The reactivity of the geminal frustrated Lewis pair (FLP) (F5C2)3SnCH2P(tBu)2 (1) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H3CC(O)CH=CH2, Ph[C(O)]2Ph, PhN=NPh and Me3SiCHN2), featuring polar or non‐polar multiple bonds and/or represent α,β‐unsaturated systems. While most adducts are formed readily, the binding of azobenzene requires UV‐induced photoisomerization, which results in the highly selective complexation of cis‐azobenzene. In the case of benzil, the reaction does not lead to the expected 1,2‐ or 1,4‐addition products, but to the non‐stereoselective (tBu)2PCH2‐transfer to a prochiral keto function of benzil. All adducts of 1 were characterised by means of multinuclear NMR spectroscopy, elemental analyses and X‐ray diffraction experiments. A highly selective complexation of cis‐azobenzene was found when reacting the isomeric compound with the intramolecular frustrated Lewis pair (F5C2)3SnCH2P(tBu)2 under UV‐induced photoisomerization conditions.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202004600