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Selone-stabilized aryltellurenyl cations

机译:克隆稳定的芳基蝶烯基阳离子

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Controlled bromination of a diarylditelluride, R2Te2 (R = 2,6-dimethylphenyl) (6) in dichloromethane led to the formation of a TeII-TeIV mixed-valent tellurenyl bromide, RBr2TeTeR (7). A further reaction of 7 with 1,3-dibutylbenzimidazolin-2-selone, C15H22N2Se (L) (9), produced the first selone adduct of the 2,6dimethylphenyltellurenyl cation with the 2,6-dimethylphenyltellurium dibromide anion, [(2,6-Me2C6H3) Te( L)](+)[(2,6-Me2C6H3)TeBr2](-)(10). The red colored cationic adduct 10 is not stable in acetonitrile and disproportionated to give the selone adduct of 2,6-dimethylphenyltellurenyl bromide, [(2,6-Me2C6H3)Te(L) Br] (11b) and bis(2,6-dimethylphenyl) tellurium dibromide, [(2,6-Me2C6H3)(2)TeBr2], (13). The metathesis reaction of 11b with AgBF4 produced a stable dark red colored selone adduct of the 2,6-dimethylphenyltellurenyl cation with the BF4- anion, [(2,6-Me2C6H3)Te(L)]+BF4-(15). The selone adducts of aryltellurenyl halides, i.e. [(2,6-Me2C6H3)Te(L)X] (X = Cl, Br, I) (11a-11c), have been synthesized by a one-pot reaction of 6 with an equimolar mixture of 9 and 1,3-dibutylbenzimidazolin-2-dihaloselones, C15H22N2SeX2 (14a-14c). Triphenylphosphine (PPh3), when treated with [(2,6-Me2C6H3)Te(L) X] (11a-11c), substitutes selone from the adduct to afford the triphenylphosphine adducts of aryltellurenyl halides, [(2,6-Me2C6H3)Te(PPh3)X] (16a-16c).
机译:二芳基二碲化物R2Te2(R = 2,6-二甲基苯基)(6)在二氯甲烷中的受控溴化作用导致形成TeII-TeIV混合价碲基溴化物RBr2TeTeR(7)。 7与1,3-二丁基苯并咪唑啉-2-硒(C15H22N2Se(L)(9)的进一步反应)生成了2,6二甲基苯基碲烯基阳离子与2,6-二甲基苯基碲二溴阴离子[[(2,6 -Me2C6H3)Te(L)](+)[(2,6-Me2C6H3)TeBr2](-)(10)。红色的阳离子加合物10在乙腈中不稳定,歧化后得到2,6-二甲基苯基碲基溴,[(2,6-Me2C6H3)Te(L)Br](11b)和bis(2,6-二甲基苯基)二溴化碲,[((2,6-Me2C6H3)(2)TeBr2],(13)。 11b与AgBF4的复分解反应生成了稳定的深红色色的2,6-二甲基苯基蝶烯基阳离子与BF4-阴离子[(2,6-Me2C6H3)Te(L)] + BF4-(15)的硒酮加合物。芳基tellurenyl卤化物的selone加合物,即[(2,6-Me2C6H3)Te(L)X](X = Cl,Br,I)(11a-11c),是通过6与一9和1,3-二丁基苯并咪唑啉-2-二卤酮的等摩尔混合物C15H22N2SeX2(14a-14c)。三苯基膦(PPh3),当用[(2,6-Me2C6H3)Te(L)X](11a-11c)处理时,从加合物中替代色氨酸,得到芳基蝶烯基卤化物的三苯基膦加合物,[(2,6-Me2C6H3) Te(PPh3)X](16a-16c)。

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