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首页> 外文期刊>Organometallics >Comparative study on ortho-C-H vs ortho-C-X (X = C, Cl, S) bond activation in ortho-C aromatic-N bond fusion in substituted anilines using ruthenium(II) mediators: Isolation and characterization of unusual Ru _2 complexes
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Comparative study on ortho-C-H vs ortho-C-X (X = C, Cl, S) bond activation in ortho-C aromatic-N bond fusion in substituted anilines using ruthenium(II) mediators: Isolation and characterization of unusual Ru _2 complexes

机译：使用钌（II）介体在取代苯胺中邻-C芳族-N键融合中邻-C-H与邻-C-X（X = C，Cl，S）键活化的比较研究：异常Ru _2配合物的分离和表征

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摘要

The chemical reactions of a selection of ortho-mono- and disubstituted anilines with two ruthenium polyene mediator complexes, CpRu ~(II)Cl(PPh 3) _2 (Cp - = cyclopentadienyl anion) and (Bnz) _2Ru ~(II) _2Cl _4 (Bnz = benzene), have been undertaken with a primary aim to make a comparison between ortho-C-H and ortho-C-X (X = Cl, C, S) bond activation processes in ortho-C-N bond fusion reactions. The reaction of ortho-monosubstituted anilines, viz., _2-chloroaniline (HL ~(1a)), _2-methylaniline (HL ~(1c)), and _2-methylthioaniline (HL ~(1b)), with CpRu ~(II)Cl(PPh 3) _2 yielded mononuclear complexes [CpRu ~(II)L _2a-cCl] (1, 3, and 5), containing in situ generated ligands N-(aryl)-ortho-quinonediimine, L ~(2a-c), along with anilido-bridged Ru ~(III) _2 complexes (2, [CpClRu ~(III){μ- η ~2-(L ~(1a)) ~-}] _2; 4, [CpClRu ~(III){μ-η ~2-(L 1c) -}] _2; and [6]Cl _2, [CpRu ~(III){μ-η ~2: η ~1-(L ~(1b)) -}] _2), respectively. The new ligands, L ~(2a-c) are formed via ortho-C-H bond activation reactions, whereas ortho-C-X bonds remained unaffected. However, the ortho-C-Cl bond activation reaction is also noted in the reaction between CpRu ~(II)Cl(PPh _3) _2 and ortho-disubstituted aniline _2,6-dichloroaniline (HL ~(3a)) in more forceful conditions. The ruthenium(~(III)) binuclear complex [CpRu ~(III){μ-η ~2: η ~1-(L ~(3a)) -}(μ-η ~2: η ~1-L ~(2d))(μ-η ~2-acetate)Ru ~(III)Cl]Cl, [7]Cl, of an in situ generated N-(2,6-dichlorophenyl)-6- chloro-ortho-quinonediimine ligand, L ~(2d), has been isolated from the above reaction. The ligand L ~(2d) coordinates in a η ~2- binding mode through an imine (=NH) nitrogen atom. The coordination mode of 2,6-dichloroanilide, (L ~(3a)) -, in [7]Cl is unusual in that an aromatic-C-Cl group is coordinated to a Ru(~(III)) center, and it represents the first authentic crystallographic evidence of such a coordination mode in a transition metal complex. Similar reactions on a redox-inert mediator complex, (Bnz) _2Ru ~(II) _2Cl _4 (Bnz = benzene), with the aforesaid aromatic amines failed to result in ortho-C-N bond fusion reactions and afforded the mononuclear anilino complexes and an anilido-bridged Ru ~(II) _2 compound, [9]Cl _2. The complexes have been characterized by using a host of physical methods as well as single-crystal X-ray structure determination. Their redox and spectroscopic properties have been thoroughly characterized by cyclic voltammetry and UV-vis and electron paramagnetic resonance spectroscopy. Density-functional theory calculations were employed to confirm their structural features and to support the spectral and redox properties.
机译：选择的邻-单和二取代苯胺与两种钌多烯介体配合物CpRu〜（II）Cl（PPh 3）_2（Cp-=环戊二烯基阴离子）和（Bnz）_2Ru〜（II）_2Cl _4的化学反应（Bnz =苯），其主要目的是比较邻-CN键融合反应中邻-CH和邻-CX（X = Cl，C，S）键活化过程。邻-单取代的苯胺，即_2-氯苯胺（HL〜（1a）），_ 2-甲基苯胺（HL〜（1c））和_2-甲基硫代苯胺（HL〜（1b））与CpRu〜（II ）Cl（PPh 3）_2生成单核络合物[CpRu〜（II）L _2a-cCl]（1、3和5），其中包含原位生成的配体N-（芳基）-邻醌二亚胺L〜（2a- c），以及苯胺桥Ru〜（III）_2配合物（2，[CpClRu〜（III）{μ-η〜2-（L〜（1a））〜-}] _2; 4，[CpClRu〜（ III）{μ-η〜2-（L 1c）-}] _2;和[6] Cl _2，[CpRu〜（III）{μ-η〜2：η〜1-（L〜（1b））- }] _2）。新的配体L〜（2a-c）通过邻-C-H键活化反应形成，而邻-C-X键保持不受影响。但是，在更强力的条件下，CpRu〜（II）Cl（PPh _3）_2与邻二取代苯胺_2,6-二氯苯胺（HL〜（3a））之间的反应中也注意到邻-C-Cl键活化反应。钌（〜（III））双核络合物[CpRu〜（III）{μ-η〜2：η〜1-（L〜（3a））-}（μ-η〜2：η〜1-L〜（ 2d））原位生成的N-（2,6-二氯苯基）-6-氯-邻苯二甲亚胺配体的（μ-η〜2-乙酸）Ru〜（III）Cl] Cl，[7] Cl，从上述反应中分离出L〜（2d）。配体L〜（2d）通过亚胺（= NH）氮原子以η〜2-结合方式进行配位。 [7] Cl中的2,6-二氯苯甲酰苯胺（L〜（3a））-的配位模式与众不同之处在于，芳族C-Cl基团与Ru（〜（III））中心配位，并且代表过渡金属络合物中这种配位模式的第一个真实的晶体学证据。在氧化还原惰性介体复合物（Bnz）_2Ru〜（II）_2Cl _4（Bnz =苯）上与上述芳族胺的类似反应未能导致邻-CN键融合反应，并提供了单核环胺基配合物和苯胺基桥联Ru〜（II）_2化合物[9] Cl _2。通过使用多种物理方法以及单晶X射线结构测定来表征复合物。它们的氧化还原和光谱性质已通过循环伏安法，紫外可见光谱和电子顺磁共振光谱法进行了全面表征。密度泛函理论计算被用来确认其结构特征并支持光谱和氧化还原特性。

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