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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Cationic Diiron and Diruthenium μ-Allenyl Complexes: Synthesis, X-Ray Structures and Cyclization Reactions with Ethyldiazoacetate/Amine Affording Unprecedented Butenolide- and Furaniminium-Substituted Bridging Carbene Ligands
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Cationic Diiron and Diruthenium μ-Allenyl Complexes: Synthesis, X-Ray Structures and Cyclization Reactions with Ethyldiazoacetate/Amine Affording Unprecedented Butenolide- and Furaniminium-Substituted Bridging Carbene Ligands

机译:阳离子二铁和钌μ-烯基络合物:合成,X射线结构和环二乙酸乙酯/胺的环化反应,提供史无前例的丁烯内酯和呋喃铵取代的桥联碳配体

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摘要

The novel cationic diiron μ-allenyl complexes [Fe_2Cp _2(CO)_2(μ-CO){μ-η~1: η~2_α,β-C_α(H)C _βC_γ(R)_2}]~+ (R = Me, 4a; R = Ph, 4b) have been obtained in good yields by a two-step reaction starting from [Fe_2Cp_2(CO)_4]. The solid state structures of [4a][CF_3SO_3] and of the diruthenium analogues [Ru _2Cp_2(CO)_2(μ-CO){μ-η~1: η~2_α,β-C_α(H)C _βC_γ(R)_2}][BPh_4] (R = Me, [2a][BPh_4]; R = Ph, [2c][BPh_4]) have been ascertained by X-ray diffraction studies. The reactions of 2c and 4a with Br?nsted bases result in formation of the μ-allenylidene compound [Ru_2Cp _2(CO)_2(μ-CO){μ-η~1:η~1- C_αC_βC_γ(Ph)_2}] (5) and of the dimetallacyclopentenone [Fe_2Cp_2(CO)(μ-CO) {μ-η~1:η~3-C_α(H)C _β(C_γ(Me)CH_2)C(O)}] (6), respectively. The nitrile adducts [Ru_2Cp_2(CO)(NCMe)(μ- CO){μ-η~1:η~2-C_α(H)C _βC_γ(R)_2}]~+ (R = Me, 7a; R = Ph, 7b), prepared by treatment of 2a,c with MeCN/Me_3NO, react with N_2CHCO_2Et/NEt_3 at room temperature, affording the butenolide-substituted carbene complexes [Ru_2Cp _2(CO)(μ-CO){μ-η~1:η~3-C _α(H)C_βC_γ(R) _2OC(O)C(H)] (R = Me, 10a; R = Ph, 10b). The intermediate cationic compound [Ru_2Cp_2(CO)(μ-CO){μ-η~1: η~3-C_α(H)C_βC _γ(Me)_2OC(OEt)C(H)]~+ (9) has been detected in the course of the reaction leading to 10a. The addition of N _2CHCO_2Et/NHEt_2 to 7a gives the 2-furaniminium-carbene [Ru_2Cp_2(CO)(μ-CO){μ- η~1:η~3-C_α(H)C _βC_γ(Me)_2OC(OEt)C(H)]~+ (11). The X-ray structures of 10a, 10b and [11][BF_4] have been determined. The reactions of 4a,b with MeCN/Me_3NO result in prevalent decomposition to mononuclear iron species.
机译:新型阳离子二铁铁-all烯基络合物[Fe_2Cp _2(CO)_2(μ-CO){μ-η〜1:η〜2_α,β-C_α(H)C_βC_γ(R)_2}]〜+(R =从[Fe_2Cp_2(CO)_4]开始,通过两步反应以高收率获得了Me,4a; R = Ph,4b)。 [4a] [CF_3SO_3]和二钌类似物[Ru _2Cp_2(CO)_2(μ-CO){μ-η〜1:η〜2_α,β-C_α(H)C_βC_γ(R) _2}] [BPh_4](R = Me,[2a] [BPh_4]; R = Ph,[2c] [BPh_4])已通过X射线衍射研究确定。 2c和4a与布朗斯台德碱的反应导致形成μ-亚烯基化合物[Ru_2Cp _2(CO)_2(μ-CO){μ-η〜1:η〜1-C_αC_βC_γ(Ph)_2}] (5)和双金属环戊烯酮[Fe_2Cp_2(CO)(μ-CO){μ-η〜1:η〜3-C_α(H)C_β(C_γ(Me)CH_2)C(O)}](6) , 分别。腈加合物[Ru_2Cp_2(CO)(NCMe)(μ-CO){μ-η〜1:η〜2-C_α(H)C_βC_γ(R)_2}]〜+(R = Me,7a; R =由MeCN / Me_3NO处理2a,c制备的Ph,7b)在室温下与N_2CHCO_2Et / NEt_3反应,得到丁烯化物取代的卡宾络合物[Ru_2Cp _2(CO)(μ-CO){μ-η〜1 :η〜3-C_α(H)C_βC_γ(R)_2OC(O)C(H)](R = Me,10a; R = Ph,10b)。中间体阳离子化合物[Ru_2Cp_2(CO)(μ-CO){μ-η〜1:η〜3-C_α(H)C_βC_γ(Me)_2OC(OEt)C(H)]〜+(9)在反应过程中检测到10a。将N _2CHCO_2Et / NHEt_2添加到7a可得到2-呋喃碳-卡宾[Ru_2Cp_2(CO)(μ-CO){μ-η〜1:η〜3-C_α(H)C_βC_γ(Me)_2OC(OEt) C(H)]〜+(11)。已经确定了10a,10b和[11] [BF_4]的X射线结构。 4a,b与MeCN / Me_3NO的反应导致普遍分解为单核铁物种。

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