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Electrochemical and Reactivity Studies of N→Sn Coordinated Distannynes
Miroslav Novák1, Tomáš Mikysek2, Aleš Růžička3
1Department of Polymer Science, University of Pardubice, 532 10, Pardubice, Czech Republic.
Abstract:
Studies are focused on the redox potentials of N→Sn coordinated distannnynes {L1-3 Sn}2 (L1 =1, L2 =2 and L3 =3, in which L1 is [C6 H3 -2,6-(Me2 NCH2 )2 ]- , L2 is [C6 H2 -2,4-tBu2 -6-(Et2 NCH2 )]- and L3 is [C6 H2 -2,4-tBu2 -6-(DippN=CH)]- ; Dipp=2,6-diisopropylphenyl), containing the tin atom in oxidation state +I. Distannynes 1-3 were used as ligands for transition metals, and complexes [{L1 Sn}2 ⋅Fe(CO)4 ] (4) and [{L2 Sn}2 ⋅Fe(CO)4 ] (5) were prepared. The set of N→Sn coordinated distannynes 1-5 was studied by cyclic voltammetry measurements and the oxidation potentials of tin atoms in 1-5 were determined. The redox potentials are influenced by either ligands L1-3 or SnI →Fe coordination. Oxidation reactions of 1-3 were also studied. The reaction of 2 with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) provided mixed organotin oxide {(L2 SnO)(L2 )Sn(μ-O)}2 (6) as a consequence of the instability of the expected {L2 Sn⋅TEMPO} complex. To support this proposed mechanism, the N→Ge coordinated digermyne {L2 Ge}2 (7) was prepared. The reaction of 7 with TEMPO provided the expected complex {L2 Ge⋅TEMPO} (8).
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