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首页> 外文期刊>Russian Chemical Bulletin >Non-symmetrically substituted ruthenocenes: synthesis, structures, and bond nature. Electronic effects of substituents in ruthenocene
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Non-symmetrically substituted ruthenocenes: synthesis, structures, and bond nature. Electronic effects of substituents in ruthenocene

机译：非对称取代的钌烯：合成，结构和键性质。钌茂金属中取代基的电子效应

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摘要

Non-symmetrically substituted ruthenocenes CpRuCpA ' (CpA ' = C5H4CHO (1a), C5H4COMe (1b), C5H4SiMe3 (1c), 1,3-C5H3(SiMe3)(2) (1d), and Cp* (1e)) were synthesized in high yields by the reaction of [CpRu(MeCN)(3)](+) with cyclopentadienide anions. The structures of complexes 1a,b,d were determined by X-ray diffraction analysis. According to the energy partition analysis data, donor substituents strengthen the interaction between the [RuCp](+) and CpA '(-) fragments, whereas acceptor substituents weaken the interaction. This bond is predominantly electrostatic (56-59%). Based on the calculated electrostatic potentials at the ruthe-nium nucleus, it is shown that the donor ability of the substituents decreases in the following order: NMe2 > NH2 > OMe > Me a parts per thousand OH > Rc > Fc a parts per thousand Allyl a parts per thousand H > SiMe3 > CH=CH2 a parts per thousand Ph > PH2 > > SH a parts per thousand F > SiH3 a parts per thousand Ca parts per thousand CH > Cl > Br a parts per thousand I a parts per thousand COOMe > COOH > COMe > CF3 > CHO > CN > NO2.
机译：合成了非对称取代的钌醚CpRuCpA'（CpA'= C5H4CHO（1a），C5H4COMe（1b），C5H4SiMe3（1c），1,3-C5H3（SiMe3）（2）（1d）和Cp *（1e）） [CpRu（MeCN）（3）]（+）与环戊二烯阴离子的反应可得到高收率。配合物1a，b，d的结构通过X射线衍射分析确定。根据能量分配分析数据，供体取代基增强了[RuCp]（+）与CpA'（-）片段之间的相互作用，而受体取代基则减弱了相互作用。该键主要是静电的（56-59％）。基于所计算的钌核上的静电势，表明取代基的供体能力按以下顺序降低：NMe2> NH2> OMe> Me千分之几OH> Rc> Fc一千分之几的烯丙基H> SiMe3> CH = CH2 a千分之几Ph> PH2 SH a千分之几F> SiH3 a千分之几Ca千分之CH> Cl> Br a千分之几I a千分之几COOMe> COOH> COMe> CF3> CHO> CN> NO2。

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