We have successfully prepared and structurally characterized five novel tin(IV) heteroleptic N,O--heteroarylalkenolates containing -CF 3 groups. The synthetic route used reactions of Sn(OtBu) 4 with 3,3,3-trifluoro(pyridin-2-yl)propen-2-ol (PyTFPH), 3,3,3-trifluoro(dimethyl-1,3-oxazol-2-yl)propen-2-ol (DMOTFPH), and 3,3,3-trifluoro(1,3-benzthiazol-2-yl)propen-2-ol (BTTFPH) in dry aprotic solvents leading to elimination of tert-butanol and formation of Sn(OtBu) 2 (PyTFP) 2 (1), Sn(OtBu) 2 (DMOTFP) 2 (2), and Sn(OtBu) 2 (BTTFP) 2 (3). The chelating ligands employed a bidentate N∩O donor set. The reactivity of OtBu groups in the obtained Sn(OtBu) 2 (N∩O) 2 complexes was further investigated in reactions with fluorinated alcohols, 2,2,2-trifluoroethanol (TFEH) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFPH). Two complexes Sn(TFE) 2 (DMOTFP) 2 (4) and [a]

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