Electrochemical synthesis of dialkylsubstituted polystannanes and their properties

Abstract

Poly(dibutylstannane) and poly(dioctylstannane) were obtained by electrochemical polymerization of dibutyldichlorostannane and dioctyldichlorostannane, respectively, in a one-compartment cell equipped with a platinum cathode and a silver anode, using tetrabutylammonium perchlorate and DME as the supporting electrolyte and the solvent, respectively.

Light‐Stability of Poly(dialkylstannane)s

“…Note that the molar mass of polystannanes might decrease somewhat upon redissolution, [10] and accordingly a moderate difference in the degradation rate might result upon exposure of solutions containing in situ synthesized or redissolved polystannanes; see, for instance, the stability factors F in Table 4 and 5 for the degradation of poly(dibutylstannane) in CH 2 Cl 2 according to both methods, where F amounted to 0.43 and 0.57, respectively. It should be noted that poly(dialkylstannane)s exhibit a strong UV absorption band with an absorption maximum in the region of 370-410 nm, [7,9,13,14,[16][17][18][19] which presumably arises from the delocalization of s-electrons of the tin atoms along the polymer backbone. In several reports, this band was used for the analysis of the degree of degradation of polystannanes.…”

“…In several reports, this band was used for the analysis of the degree of degradation of polystannanes. [7,[17][18][19] However, as polystannanes are sensitive to light, some degradation might be induced by the light employed for the UV-Vis measurements. We investigated the extent of this degradation with poly-(dibutylstannane), poly(dioctylstannane), and poly(didodecylstannane) in toluene solutions at a concentration of ca.…”

Oriented Poly(dialkylstannane)s

“…[1][2][3][4][5][6][7][8][9][10] These polymers, which typically are of the composition (-SnR 2 -) n and termed polystannanes, are structurally related to corresponding polymers with the semi-metals silicon or germanium (i.e., elements that are located in the periodic table in the same group as tin) and are of potential interest as semiconductors. [11][12][13] However, the synthesis of linear polystannanes in high yield and free of cyclic oligomers has been achieved only recently [2,3] and, therefore, until now the properties of polystannanes have been relatively little explored.…”

Organometallic Polymers of Germanium, Tin and Lead

“…Electrochemical reduction of diorganotin dihalides is expected to be the most important approach for the large-scale preparation of polystannanes 22. However, so far only (n-Bu 2 Sn) n and (n-Oct 2 Sn) n were prepared by electrochemical synthesis 95 (Table 5, Scheme 15). The reactions were carried out in 1,2-dimethoxyethane (DME) as solvent and with tetrabutylammonium perchlorate as supporting electrolyte.…”

“…In air, solid samples decompose very slowly and poly(diaryl)stannanes are air-stable over at least several weeks in the dark. No decomposition of H(n-Bu 2 Sn) n H in pentane took place, even when oxygen was bubbled through its solution 95 . It was concluded that polystannanes are stable towards oxygen but extremely reactive to moisture.…”