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首页> 外文期刊>Chemistry: A European journal >Intramolecular Tetrylene Lewis Adducts: Synthesis and Reactivity
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Intramolecular Tetrylene Lewis Adducts: Synthesis and Reactivity

机译：分子内四甲苯刘易斯加合物：合成与反应性

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摘要

A series of benzyl(diphenylphosphino) and o-phenyl(diphenlyphosphino) substituted germylenes and plumbylenes were synthesized by nucleophilic substitution between the respective lithium reagent and tetrylene halide. The Lewis pairs were characterized by X-ray crystallography and NMR spectroscopy. The reactivity of the tetrylenes was investigated with respect to azide addition. In the germylene case, the germaniumimide was formed as the kinetically controlled product, which rearranges upon heating to give the phosphinimide. The stannylene and plumbylene derivatives react with adamantylazide to give the azide adducts. 1-Pentene reacts diastereoselectively with the phosphagermirane to give a cyclic addition product. Trimethysilylacetylene shows an addition with the benzylphosphino- substituted germylene and plumbylene to give the cycloheteropentene molecules. The addition product between phenylacetylene and the four membered Ge-P adduct shows after addition at room temperature a 1,4-phenylmigration to give a cyclic phosphine. Alkylnitrene insertion into a Ge-C bond of the alkyne addition product of the phosphagermirane was found in reaction with adamantylazide.
机译：通过在各自的锂试剂和四甲苯卤化物之间进行亲核取代，合成了一系列的苄基（二苯基膦基）和邻苯基（二苯基膦基）取代的亚二甲苯基和亚苄基。通过X射线晶体学和NMR光谱表征路易斯对。关于叠氮化物的添加，研究了四甲苯的反应性。在亚二甲基case的情况下，形成锗酰亚胺作为动力学控制的产物，其在加热时重新排列以给出次膦酰亚胺。亚锡和亚b衍生物与金刚烷基叠氮化物反应，得到叠氮化物加合物。 1-戊烯与磷杂芳烃非对映选择性地反应，得到环状加成产物。三甲基甲硅烷基乙炔显示出与苄基膦取代的亚二甲苯基和1，2，5-二甲苯基的加成，得到环杂戊烯分子。苯乙炔与四元Ge-P加合物之间的加成产物在室温下添加后显示出1,4-苯基迁移，生成环状膦。在与金刚烷基叠氮化物的反应中发现了烷基亚硝烯插入到磷酰亚胺的炔烃加成产物的Ge-C键中。

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