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首页> 外文期刊>Chemistry: A European journal >Reactivity of a silylsilylene bearing a functionalized diaminochlorosilyl substituent
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Reactivity of a silylsilylene bearing a functionalized diaminochlorosilyl substituent

机译：带有官能化二氨基氯甲硅烷基取代基的甲硅烷基亚甲硅烷基的反应性

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摘要

The reactivity of the silylsilylene [{PhC(NtBu)_2}SiSi(Cl){(NtBu) _2C(H)Ph}] (2) towards diphenylacetylene, azobenzene, 2,6-diisopropylphenyl azide, sulfur, and selenium is described. The reaction of 2 with one equivalent of azobenzene in toluene afforded compound 3, which is the first example of a 1,2-diaza-3,4-disilacyclobutane containing a pentacoordinate silicon center. The formation of 3 can be explained by a [1+2] cycloaddition of the divalent Si center in 2 with PhN=NPh to form a diazasilacyclopropane intermediate, which then undergoes a 1,2-chlorine shift to release the ring strain to form 3. Similarly, the reaction of 2 with one equivalent of diphenylacetylene in toluene afforded the 1,2-disilacyclobutene 4, which contains a pentacoordinate silicon center. The reaction of 2 with 1.6equivalents of 2,6-diisopropylphenylazide in toluene afforded the silaimine [LSi(=NAr)N(Ar)L′] (5, L=PhC(NtBu)_2, L′=Si(Cl){(NtBu) _2C(H)Ph}, Ar=2,6-iPr_2C_6H_3). The formation of 5 can be explained by an oxidative addition of the divalent Si center in 2 with ArN_3 to afford a silaimine intermediate, which then reacts with another molecule of ArN_3 to give compound 5. The reaction of 2 with elemental sulfur in toluene afforded the chlorosilanethione [LSi(S)Cl] (6) and dithiodisiletane [{Ph(H)C(NtBu)_2}Si(μ-S)] _2 (7). Treatment of 2 with elemental selenium in THF afforded the di(silaneselone) [LSi(Se)Si(Se)L] (8). Evidently, the divalent Si center in 2 undergoes oxidative addition with chalcogens to afford a silylsilanechalcogenone intermediate, which then displaces ":Si{(NtBu)_2C(H)Ph}" and "ClSi{(NtBu)_2C(H)Ph}" to form 6 and 8, respectively. Moreover, compound 8 was synthesized by the reaction of [{PhC(NtBu) _2}Si:]_2 (10) with elemental selenium in THF. The results show that the reactions of 2 are initiated by oxidative addition of the divalent silicon center, and then the intermediate formed undergoes a rearrangement involving the diaminochlorosilyl substituent to form compounds 3-8. These products have been characterized by NMR spectroscopy and X-ray crystallography. Stable silylenes: The reactivity of the silylsilylene 1 towards diphenylacetylene, azobenzene, 2,6-diisopropylphenyl azide, sulfur, and selenium is reported. The results show that the reactions of 1 are initiated by oxidative addition of the divalent silicon center, and then the intermediate formed undergoes a rearrangement that involves the diaminochlorosilyl substituent (see scheme). The diaminochlorosilyl substituent in 1 can undergo a 1,2-chlorine shift, and it also serves as a leaving group in the reactions.
机译：描述了甲硅烷基甲硅烷基[{PhC（NtBu）_2} SiSi（Cl）{（NtBu）_2C（H）Ph}]（2）对二苯基乙炔，偶氮苯，2,6-二异丙基苯基叠氮化物，硫和硒的反应性。 2与一当量甲苯中的偶氮苯反应，得到化合物3，该化合物为含有五配位硅中心的1,2-二氮杂3,4-二硅环丁烷的第一个实例。 3的形成可以通过将2中的二价Si中心与PhN = NPh进行[1 + 2]环加成反应形成二氮杂硅环丙烷中间体，然后进行1,2-氯转移以释放环应变以形成3类似地，2与一当量二苯乙炔在甲苯中的反应得到1，2-二硅环丁烯4，其含有五配位硅中心。 2与1.6当量的2,6-二异丙基苯基叠氮化物在甲苯中的反应得到硅亚胺[LSi（= NAr）N（Ar）L']（5，L = PhC（NtBu）_2，L'= Si（Cl）{ （NtBu）_2C（H）Ph}，Ar ＝ 2,6-iPr_2C_6H_3）。 5的形成可以通过2中的二价Si中心与ArN_3的氧化加成得到硅亚胺中间体，然后与另一分子ArN_3反应得到化合物5来解释。2与元素硫在甲苯中的反应得到氯硅烷硫酮[LSi（S）Cl]（6）和二硫代二iletane [{Ph（H）C（NtBu）_2} Si（μ-S）] _2（7）。在THF中用元素硒处理2，得到二（硅烷硒酮）[LSi（Se）Si（Se）L]（8）。显然，2中的二价Si中心与硫族元素进行氧化加成反应，得到甲硅烷基硅烷硫属酮中间体，然后取代“：Si {（NtBu）_2C（H）Ph}”和“ ClSi {（NtBu）_2C（H）Ph}”分别形成6和8。此外，通过[{PhC（NtBu）_2} Si：] _ 2（10）与元素硒在THF中的反应合成了化合物8。结果表明2的反应通过二价硅中心的氧化加成而引发，然后形成的中间体发生重排，涉及二氨基氯甲硅烷基取代基以形成化合物3-8。这些产物已经通过NMR光谱和X射线晶体学表征。稳定的甲硅烷基：据报道，甲硅烷基甲硅烷基1对二苯基乙炔，偶氮苯，2,6-二异丙基苯基叠氮化物，硫和硒具有反应性。结果表明1的反应通过二价硅中心的氧化加成而引发，然后形成的中间体发生重排，该重排涉及二氨基氯甲硅烷基取代基（参见方案）。 1中的二氨基氯甲硅烷基取代基可发生1,2-氯转移，并且在反应中也用作离去基团。

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