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)(3)SnCH2P(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)](2)Ph, PhN=NPh and Me3SiCHN2), featuring polar or non-polar multiple bonds and/or represent alpha,beta-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)(2)PCH2-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.