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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis of 13-vertex dimetallacarboranes by electrophilic insertion into 12-vertex ruthenacarboranes
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Synthesis of 13-vertex dimetallacarboranes by electrophilic insertion into 12-vertex ruthenacarboranes

机译：用电泳插入13-顶点Dimetallacarboranes的12-顶点钌酰胺酰烷基

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摘要

The electrophilic insertion of organometallic species into metallacarboranes was studied in detail for the model compound - the 12-vertex closo-ruthenacarborane anion [Cp*Ru(C2B9H11)](-)(1). Reactions of the anion 1 with the 12-electron cationic species [M(ring)](+) (M(ring) = RuCp, RuCp* and Co(C4Me4)) gave the 13-vertex closo-dimetallacarboranes Cp*Ru(C2B9H11) M(ring). Similar reactions of the neutral ruthenacarborane Cp*Ru(Me2S-C2B9H10) produce the cationic dimetallacarboranes [Cp*Ru(Me2S-C2B9H10) M(ring)]+. The symmetrical 13-vertex diruthenacarboranes (C5R5) Ru(R2C2B9H9) Ru(C5R5) can be prepared by the direct reactions of Tl-2[7,8-R-2-7,8-C2B9H9] (R = H and Me) with two equivalents of [CpRu(MeCN)(3)](+) or [Cp*RuCl](4). The insertions of the 14-electron cationic species [M(ring)](+) (M(ring) = NiCp, NiCp* and Co(C6Me6)) into 1 gave the 13-vertex dimetallacarboranes Cp*Ru(C2B9H11) M(ring), which have a distorted framework with one open face. The structures of Cp*Ru(C2B9H11) Co(C4Me4) and Cp*Ru(C2B9H11) NiCp were established by X-ray diffraction. Some of the 13-vertex dimetallacarboranes have two electrons less than required by Wade's rules. This violation is explained by the absence of the appropriate pathway for the distortion of the framework.
机译：为模型化合物研究了有机金属物种将有机金属物质的亲热插入金属酰胺酰胺 - 12-顶点型号 - 钌酰胺阴离子[CP * Ru（C2B9H11）]（ - ）（1）。阴离子1与12 - 电子阳离子物质的反应[M（环）]（+）（m（环）= RUCP，RUCP *和CO（C4ME4））给出了13-顶点赛·二维酰氯酰烷CP * Ru（C2B9H11 ）m（戒指）。中性钌酰基硼烷CP * Ru（Me2S-C2B9H10）的类似反应产生阳离子二萜酰基烷基[CP * Ru（Me2S-C2B9H10）M（环）] +。对称的13-顶点Driuthenacarboranes（C5R5）Ru（R2C2B9H9）Ru（C5R5）可以通过TL-2的直接反应制备[7,8-R-2-7,8-C2b9H9]（R = H和ME）具有两当量[Cpru（MECN）（3）]（+）或[CP * RUCL]（4）。 14 - 电子阳离子物质[M（环）]（+）（+）（m（环）= Nicp，NicP *和Co（C6ME6））的插入为1给出13-顶点DiMetallacarboranes CP * Ru（C2B9H11）M（戒指），具有一个开口面的扭曲框架。通过X射线衍射建立CP * Ru（C2B9H11）CO（C4ME4）和CP * Ru（C2B9H11）NICP的结构。其中一些13顶点Dimetallacarboranes有两个电子比韦德规则所需的电子。由于框架扭曲的缺陷，缺乏这种违规方式解释。

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