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首页> 外文期刊>Organometallics >Template Synthesis of Ruthenium Complexes with Saturated and Benzannulated NH,NH-Stabilized N-Heterocyclic Carbene Ligands
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Template Synthesis of Ruthenium Complexes with Saturated and Benzannulated NH,NH-Stabilized N-Heterocyclic Carbene Ligands

机译:饱和和苯甲酰化NH,NH稳定的N-杂环碳烯配体钌配合物的模板合成

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摘要

Reaction of [RuCl2(p-cymene)](2) with 2-azidoethyl isocyanide (1a) or 2-azidophenyl isocyanide (1b) leads to the isocyanide complexes [RuCl2(p-cymene)(1a)] [2a] and [RuCl2(p-cymene)(1b)] [2b], respectively. Complex [2a] reacts with triphenylphosphine to yield the complex with a phosphinimine-substituted isocyanide ligand [3]. The attempted hydrolysis of the phosphinimine group in [3] with HCl center dot Et2O produced the complex with a protonated phosphinimine ligand [4]Cl instead of the expected complex with a 2-aminoethyl isocyanide ligand. An alternative method for the reduction of the azido group in [2a] and [2b] using FeCl3/NaI has been applied leading to complexes with the 2-amino-substituted isocyanide ligands, which undergo intramolecular ring closure to yield the complexes of type [RuI2(P-cymene)(NHC)], [5a] and [5b].
机译:[RuCl2(p-cymene)(2a)]与2-叠氮基乙基异氰化物(1a)或2-叠氮基苯基异氰酸酯(1b)的反应生成异氰酸酯络合物[RuCl2(p-cymene)(1a)] [2a]和[ RuCl2(p-cymene)(1b)] [2b]。配合物[2a]与三苯基膦反应,得到具有亚膦酰胺取代的异氰化物配体[3]的配合物。尝试用HCl中心点Et2O水解[3]中的膦亚胺基团,生成的化合物与质子化的膦亚胺配体[4] Cl形成复合物,而不是预期的与2-氨基乙基异氰化物配体的复合物。已经应用了另一种使用FeCl3 / NaI还原[2a]和[2b]中叠氮基的方法,该方法可导致与2-氨基取代的异氰酸酯配体形成络合物,并对其进行分子内闭环反应,从而生成[III]型络合物。 RuI 2(对苯甲基)(NHC)],[5a]和[5b]。

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