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(CH(2)CMe(2)O)(3)SnX (1, X = Ot-Bu; 2, X = Oi-Pr; 3, X = 2,6-Me(2)C(6)H(3)O; 4, X = p-t-BuC(6)H(4)O; 5, X = p-NO(2)C(6)H(4)O; 6, X = p-FC(6)H(4)O; 7, X = p-PPh(2)C(6)H(4)O; 8, X = p-MeC(6)H(4)S; 9, X = o-NH(2)C(6)H(4)O; 10, X = OCPh(2)CH(2)NMe(2); 11, X = Ph(2)P(S)S; 12, X = p-t-BuC(6)H(4)C(O)O; 13, X = Cl; 14, X = Br; 15, X = I; 16, X = p-N(CH(2)CMe(2)O)(3)SnOSiMe(2)C(6)H(4)SiMe(2)O) are reported. The compounds are characterized by X-ray diffraction analyses (3-8, 11-16), multinuclear NMR spectroscopy, (13)C CP MAS (14) and (119)Sn 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(+•), 8(+•), and 13(+•), respectively.
Lehrstuhl für Anorganische Chemie II der Technischen Universität Dortmund, D-44221 Dortmund.
Thomas
T
Zöller
Christina
C
Dietz
Ljuba
L
Iovkova-Berends
Olga
O
Karsten
Gerrit
G
Bradtmöller
Ann-Kristin
AK
Wiegand
Yu
Y
Wang
Viatcheslav
V
Jouikov
Klaus
K
Jurkschat