6533b7cefe1ef96bd1256f8a

RESEARCH PRODUCT

Investigations on organoantimony compounds

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Abstract Trichlorodiorganoantimony(V) compounds, R2SbCl3, in which the antimony atom is part of a heterocyclic ring have been synthesized. They have been converted into the corresponding tetramethylammonium tetrachlorodiorganoantimonates, [R2SbCl4]− [Me4N]+, which are hexacoordinate diorganoantimony(V) species in which the antimony-carbon bonds are forced into a cis-position. 5,5,5-Trichlorodibenzostibole, 10,10,10-trichlorophenoxantimonin, 5,5,5-trichloro-5,10-dihydrodibenz[b, e]antimonin and 5,5,5-trichloro-10,11-dihydro-5H-dibenzo[b, f]stibepin have been prepared by chlorination of the corresponding heterocyclic chlorodiarylstibines. Heterocyclic trichlorodialkylantimony(V) compounds have been prepared by a reaction sequence involving the chlorination of the corresponding heterocyclic distibines. Treatment of 1-methylstibolane (1-methylstibacyclopentane) or 1-methylantimonane (1-methylstibacyclohexane) with sodium in liquid ammonia results in the almost exclusive cleavage of the antimony-methyl carbon bond to give sodium antimonides, which on treatment with 1,2-dichloroethane give the corresponding heterocyclic distibines, 1,1′-bistibolane and 1,1′-biantimonane. Upon treatment with sulphuryl chloride in a 1 3 molar ratio these heterocyclic distibines give 1,1,1-trichlorostibolane and 1,1,1-trichloroantimonane, respectively. The trivalent heterocyclic monochlorostibines 1-chlorostibolane and 1-chloroantimonane have been prepared analogously by reaction of the corresponding distibines with sulphuryl chloride in a 1 1 molar ratio. Complexes of the types [cis-R2SbCl4]− [Me4N]+ were readily obtained from the 1 1 reaction of compounds cis-R2SbCl3 with tetramethylammonium chloride, but the seven-membered heterocyclic antimony compound 5,5,5-trichloro-10,11-dihydro-5H-dibenzo[b, f]stibepin is unreactive because of steric hindrance around the antimony atom. The complexes [(CH2)nSbCl4]− [Me4N]+ (n = 4, 5) decompose slowly in methanol with formation of [Sb2Cl9]3− [Me4N]3+. IR data of the various compounds are reported.