Stepwise Oxidation of the Stannole Dianion

Abstract

Tin oxidation of stannole dianion 1 with 1.3 equivalents of oxygen gave terstannole-1,3-dianion 3. The non-aromatic nature of 3 was confirmed by X-ray crystallographic analysis. Treatment of 1 with 1,2-dibromoethane (3 equiv) gave poly(1,1-stannole) 4, the formation of which was proven by reduction of 4 with lithium to revert to the starting dianion 1. Reaction of 1 with 1,2-dibromoethane (3 equiv) in the presence of phenyllithium gave phenyl-capped ter(1,1-stannole) 7. The electronic absorption spectra of newly obtained stannoles were also measured.

1,1′-Di-tert-butyl-2,2′,3,3′,4,4′,5,5′-octaethyl-1,1′-bistannole

“…Poly(1,1-germole)s have also been synthesized (Sohn et al, 2003). In contrast, as for tin analogues, only a few reports on the synthesis of oligo(1,1-stannole)s have appeared, so far (Haga et al, 2008). We report herein the molecular structure of the title compound, which is a novel bi(1,1-stannole) bearing ethyl groups on the carbon atoms of the five-membered rings.…”

“…For the synthesis and X-ray diffraction analysis of bi(1,1stannole)s whose carbon atoms of the five-membered rings have phenyl groups, see: Saito et al (2002. For related literature on bi-, oligo-and poly-(1,1-metallole)s, see: Haga et al (2008); Kanno et al (1998); Kim & Woo (2002); ; Saito et al (2010); Sohn et al (1999Sohn et al ( , 2003; Yamaguchi & Tamao (1998); Yamaguchi et al (1997Yamaguchi et al ( , 1999. T = 100 K 0.25 Â 0.10 Â 0.05 mm…”

“…(2011). E67, m949 The group 14 metalloles has received much attention as good precursors of their polymers that reveal interesting optical properties (Yamaguchi et al, 1998;Haga et al, 2008) as well as their anion species, which are heavier congeners of the cyclopentadienyl anion . After the synthesis of several oligo(1,1-silole)s and poly(1,1-silole)s (Yamaguchi et al, 1997(Yamaguchi et al, , 1999; Kanno et al, 1998;Sohn et al, 1999), they have been used as building blocks of organic electroluminescent devices (Kim & Woo (2002)).…”

Syntheses and Properties of Tin‐Containing Conjugated Heterocycles

“…[36] If 11 was reactedw ith different quantities of oxidizing agents, it afforded 1,2-dilithiobistannoles 68,1 ,3-dilithioterstannoles 69 and the unstable poly(1,1-stannole) 70 (Scheme 21). [59] The Sn-tert-butyl-Sn-lithiostannole 64 a can reactw ith MeI to produce 71 or,i fi ti se xposed to air,1 ,1-bistannoles 72 (Scheme 22). [33a] When the stannole monoanion 14 reacted with 1,6-dibromohexane, bis(stannole) 73 was formed in which the two rings are connected by an alkyl chain (Scheme23); this is contrary to the reaction of the dianionic stannole 11.…”

“…Reactions of the dilithiostannole 11 with oxidizinga gents. [59] Scheme22. Another example was the reactionoft he spirotin compound 81 with the ambiphilic reagent trimethyltin ethoxide (Scheme 26).…”