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首页> 外文期刊>Chemistry: A European journal >eta~6-Mesityl, eta~1-Imidazolinylidene-Carbene-Ruthenium(II) Complexes: Catalytic Activity of their Allenylidene Derivatives in Alkene Metathesis and Cycloisomerisation Reactions
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eta~6-Mesityl, eta~1-Imidazolinylidene-Carbene-Ruthenium(II) Complexes: Catalytic Activity of their Allenylidene Derivatives in Alkene Metathesis and Cycloisomerisation Reactions

机译：η〜6-Mesityl，η〜1-咪唑啉-碳烯-钌（II）配合物：它们的亚烯基衍生物在烯烃复分解和环异构化反应中的催化活性

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摘要

The reaction of electron-rich carbene-precursor olefins containing two imidazolinylidene moieties [(2,4,6-Me_3C_6H_2CH_2)NCH_2CH_2N(R)C=]_2 (2a: R = CH_2CH_2OMe, 2b R = CH_2Mes), bearing at least one 2,4,6-trimethylbenzyl (R = CH_2Mes) group on the nitrogen atom, ith [RuCl_2(arene)]_2 (arene = p-cymene, hexamethylbenzene) selectively leads to two types of complexes. The cleavage of the chloride bridges occurs first to yield the expected (carbene) (arene)ruthenium(II) complex 3. Then a further arene displacement reaction takes place to give the chelated eta~6-mesity, eta~1-carbene-ruthenium complexes 4 and 5. An analogous eta~6-a-rene,eta~1-carbene complex with a benzimidazole frame 6 was isolated from an in situ reaction between [RuCl_2(p-cymene)_2, the corresponding benzimidazolium salt and cesium carbonate. On heating, the RuCl_2(imidazolinylidene) (p-cymene) complex 8, with p-methoxybenzyl pendent groups attached to the N atoms, leads to intramolecular p-cymene displacement and to the chelated eta~6-arene, eta~1-carbene complex 9. On reaction with AgOTf and the proparglyic alcohol HC ident to CCPh_2H, compounds 4-6 were transformed into the corresponding ruthenium allylidene intermediates (4->10, 5->11, 6->12). The in situ generated intermediates 10-12 were found to be active and selective catalysts for ring-closing metathesis (RCM) or cyclioisomerisation reactions depending on the nature of the 1,6-dienes. Two complexes [RuCl_2{eta~1-CN(CH_2C_6H_2Me_3-2,4,6)CH_2CH_2N-(CH_2CH_2OMe)}(C_6Me_6)] 3 with a monodentate carbene ligand and [RuCl_2{eta~1-CN[CH_2(eta~6-C_6H_2Me_3-2,4,6)]CH_2CH_2N(CH_2C_6H_2Me_3-2,4,6)}] 5 with a chelating carbene-arene ligand were characterised by X-ray crystallography.
机译：包含两个咪唑啉亚叉基部分[（2,4,6-Me_3C_6H_2CH_2）NCH_2CH_2N（R）C =] _ 2（2a：R = CH_2CH_2OMe，2b R = CH_2Mes）的富电子卡宾前体烯烃的反应氮原子上的，4,6-三甲基苄基（R = CH_2Mes）基团[RuCl_2（芳烃）] _ 2（芳烃=对苯甲基，六甲基苯）选择性地产生两种类型的络合物。首先发生氯化物桥的裂解，以产生预期的（碳烯）（芳烃）钌（II）络合物3。然后发生进一步的芳烃置换反应，得到螯合的η-6异构体，ηη-1碳烯钌。配合物4和5。从[RuCl_2（p-cymene）_2]，相应的苯并咪唑鎓盐和碳酸铯之间的原位反应中分离出具有苯并咪唑骨架6的类似eta〜6-a-rene，eta〜1-卡宾配合物。加热后，RuCl_2（咪唑啉基）（对伞花烃）配合物8与对甲氧基苄基侧基连接在N原子上，导致分子内对伞花烃置换，并导致螯合的eta〜6-芳烃，η〜1-卡宾配合物9。在与AgOTf和与CCPh_2H相同的炔丙醇HC反应时，化合物4-6被转化为相应的钌烯丙基亚烷基中间体（4-> 10、5-> 11、6-> 12）。发现原位产生的中间体10-12是活性的，并且取决于1，6-二烯的性质，用于闭环复分解（RCM）或环异构化反应的选择性催化剂。具有单齿卡宾配体和[RuCl_2 {eta〜1-CN [CH_2（eta〜6）]的两个络合物[RuCl_2 {eta〜1-CN（CH_2C_6H_2Me_3-2,4,6）CH_2CH_2N-（CH_2CH_2OMe）}（C_6Me_6）] 3用X射线晶体学表征具有螯合卡宾-芳烃配体的-C_6H_2Me_3-2,4,6）] CH_2CH_2N（CH_2C_6H_2Me_3-2,4,6）}] 5。

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