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The reactivity of the geminal frustrated Lewis pair (FLP) (F5 C2 )3 SnCH2 P(tBu)2 (1) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H3 CC(O)CH=CH2 , Ph[C(O)]2 Ph, PhN=NPh and Me3 SiCHN2 ), 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