Novel Stannatranes of the Type N(CH2CMe2O)3SnX (X = OR, SR, OC(O)R, SP(S)Ph2, Halogen). Synthesis, Molecular Structures, and Electrochemical Properties

The syntheses of the stannatrane derivatives of the type N(CH2CMe2O)(3)SnX (1, X = Ot-Bu; 2, X = Oi-Pr; 3, X = 2,6-Me2C6H3O; 4, X = p-t-BuC6H4O; 5, X = p-NO2C6H4O; 6, X = p-FC6H4O; 7, X = p-PPh2C6H4O; 8, X = p-MeC6H4S; 9, X = o-NH2C6H4O; 10, X = OCPh2CH2NMe2; 11, X = Ph2P(S)S; 12, X = p-t-BuC6H4C(O)O; 13, X = Cl; 14, X = Br; 15, X = I; 16, X = p-N(CH2CMe2O)(3)SnOSiMe2C6H4SiMe2O) are reported. The compounds are characterized by X-ray diffraction analyses (3-8, 11-16), multinuclear NMR spectroscopy, C-13 CP MAS (14) and Sn-119 CP MAS NMR (13, 14) spectroscopy, mass spectrometry and osmometric molecular weight determination (13). Electrochemical measurements show that anodic oxidation of the stannatranes 4 and 8 occurs via electrochemically reversible electron transfer resulting in the corresponding cation radicals. The latter were detected by cyclic voltammetry (CV) and real-time electron paramagnetic resonance spectroscopy (EPR). DFT calculations were performed to compare the stannatranes 4, 8, and 13 with the corresponding cation radicals 4(+center dot), 8(+center dot), and 13(+center dot), respectively.