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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Bis(amidinato)- and bis(guanidinato)silylenes and silylenes with one sterically demanding amidinato or guanidinato ligand: synthesis and reactivity
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Bis(amidinato)- and bis(guanidinato)silylenes and silylenes with one sterically demanding amidinato or guanidinato ligand: synthesis and reactivity

机译:双(氨基氨基) - 和双(胍)甲硅烷甲硅烷基和甲硅烷甲硅烷醇,一个小苛刻的氨基氨基或胍蛋白酶:合成和反应性

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This article deals with the synthesis and reactivity of the bis(amidinato)silylene [iPrNC(Ph)NiPr](2)Si (5), the bis(guanidinato) silylene [iPrNC(NiPr2)NiPr](2)Si (6), the mono(amidinato)silylene [DippNC(Ph)NDipp]SiNMe2 (Dipp = 2,6-diisopropylphenyl) (8) and the mono(guanidinato) silylene [DippNC(NMe2)NDipp]SiN(SiMe3)(2) (9). The reactions studied include (i) nucleophilic substitutions, (ii) Lewis acid/base reactions, (iii) Bronsted acid/base reactions, (iv) oxidative additions (bond activations, small-molecule activations), (v) cycloaddition reactions with unsaturated organic substrates, (vi) reductions and (vii) radical formation by muonium addition. Silylenes 5, 6, 8 and 9 have been demonstrated to display unique reactivity profiles and to be versatile precursors for the synthesis of novel four-or five-coordinate silicon(II) and four-, five- or six-coordinate silicon(IV) complexes with unprecedented structural motifs. This article also deals with the structural characterisation of all the new silicon(II) and silicon(IV) compounds synthesised. Crystal structure analyses and Si-29 NMR spectroscopic studies in the solid state and in solution were used to characterise the silicon coordination polyhedra of these compounds.
机译:本文涉及双(脒基)甲硅烷基醚的合成和反应性[IPRNC(pH)NIPR](2)Si(5),双(胍)甲硅烷基醚[IPRNC(NIPR2)NIPR](2)Si(6) ,单甲基甲硅烷基甲硅烷基甲基甲基甲基甲酸钠[Dippnc(pH)] SINME2(DIPP = 2,6-二异丙基苯基)(8)和单甲基甲基甲苯基甲硅烷基甲基甲基甲硅烷基(SIME3)(2)(9 )。所研究的反应包括(i)亲核取代,(ii)路易斯酸/碱反应,(III)富烷酸/碱反应,(IV)氧化添加(键活化,小分子激活),(v)与不饱和的环加成反应通过加法加入有机基质,(VI)减少和(VII)自由基形成。已经证明甲硅烷基5,6,8和9,以显示独特的反应性谱,并是用于合成新的四个或五坐标硅(II)和四个,五个或六个坐标硅(IV)的通用前体复合物与前所未有的结构主题。本文还涉及合成的所有新硅(II)和硅(IV)化合物的结构表征。使用固态和溶液中的晶体结构分析和Si-29 NMR光谱研究表征这些化合物的硅配位多面体。

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