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Steric Control over Arene Coordination to #beta#-Diiminate Rhodium (I) Fragments

机译:芳烃配位控制到#beta#-Rhodium(I)片段的立体控制。

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摘要

The bulky ligands L_x~- (L_x = (2,6-C_6H_3X_2)NC(Me)CHC(Me)CHC(Me)N(2,6-C_6H+3X_2), X = Cl, Me) can be used to generate the fluxional mononuclear arene complexes [L_xRh(#eta#~4-arene)] (arene = benzene, toluene, m-xylene, mesitylene), which for X = Me disproportionate to fluxional dinuclear complexes [{L_MeRh}_2 (anti-#mu#-arene)]. For both mononuclear and dinuclear complexes, steric interactions do not stop the fluxionality but govern the preferred orientation of the methyl-substitute darenes, thus allowing indirect determination of the static NMR parameters. For the #mu#-arene complexes, two distinct types fo fluxionality are propsoed on the basis of calculatiosn: ring rotation adn metal shift. In the solid state, the toluene complex has an #eta#~
机译:庞大的配体L_x〜-(L_x =(2,6-C_6H_3X_2)NC(Me)CHC(Me)CHC(Me)N(2,6-C_6H + 3X_2),X = Cl,Me)可用于生成通量单核芳烃络合物[L_xRh(#eta#〜4-芳烃)](芳烃=苯,甲苯,间二甲苯,均三甲苯),对于X = Me,它与通量双核络合物[{L_MeRh} _2(反# mu#-arene)]。对于单核和双核配合物,空间相互作用都不会阻止流动性,而是支配了甲基取代烯的优选取向,因此可以间接确定静态NMR参数。对于#mu#-芳烃配合物,基于计算方法提出了两种不同的流动性类型:环旋转和金属位移。在固态下,甲苯络合物具有#eta#〜

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