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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Reactions of organo-rhodium complexes with multidentate N,N and N,S-heterocycles and exchange studies by NMR
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Reactions of organo-rhodium complexes with multidentate N,N and N,S-heterocycles and exchange studies by NMR

机译：有机铑配合物与多齿N，N和N，S-杂环的反应以及NMR交换研究

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摘要

Dihalobridged binuclear complexes [Rh(diolefin)(mu-X)](2) (diolefin = 1,5-cyclooctadiene (cod), X = Cl or Br: diolefin = norbornadiene (nbd), X = Cl), undergo halide bridge cleavage reactions with multidentate N,N-heterocycles 1,3,5-tris(benzimidazolyl)benzene ((LH3)-H-1), 1,3,5-tris(N-methylbenzimidazolyl)benzene ( (LH3)-H-2) and N,S-heterocycle 1,3,5-tris(benzothiazolyl)benzene ((LH3)-H-3) to yield trinuclear heterocycle bridged complexes [{RhX(cod)}(3)(mu-LH3)] and [{RhCl(nbd)}(3)(mu-LH3)] (LH3 = (LH3)-H-1, (LH3)-H-2, (LH3)-H-3). H-1 NMR exchange measurements have shown resonances for olefinic protons 1 '', 2 '', 5 '' and 6 '' of cod at different chemical shifts, perhaps due to restricted Rh-N bond rotation. The olefinic and aliphatic protons would undergo exchange with each other and also with intermediate species. The exchange mechanism may be visualized to involve Rh-N bond breaking, rotation of the cod ligand of the T-shaped (three-coordinate) intermediate species followed by recomplexation. An alternate mechanism may be Rh-cod bond breaking at olefin positions 5 '' and 6 ''. isomerisation of the T-complex such that 5 ''/6 '' moves trails to X coupled with rotation of the heterocycle about the Rh-N bond (made easier by the reduced coordination number of the intermediate), followed by recoordination of 1 ''/2 '' trans to N, followed by recomplexation. NMR signals from the intermediate species in one dimensional H-1, C-13 and 2D NMR spectra have supported the exchange of protons.
机译：二卤代双核络合物[Rh（二烯烃）（mu-X）]（2）（二烯烃= 1,5-环辛二烯（鳕鱼），X = Cl或Br：二烯烃=降冰片二烯（nbd），X = Cl），经过卤化物桥多齿N，N-杂环1,3,5-三（苯并咪唑基）苯（（LH3）-H-1），1,3,5-三（N-甲基苯并咪唑基）苯（（LH3）-H- 2）和N，S-杂环1,3,5-三（苯并噻唑基）苯（（LH3）-H-3）生成三核杂环桥联配合物[{RhX（cod）}（3）（mu-LH3）]和[{RhCl（nbd）}（3）（mu-LH3）]（LH3 ＝（LH3）-H-1，（LH3）-H-2，（LH3）-H-3）。 H-1 NMR交换测量结果表明，在不同化学位移下，鳕鱼的烯烃质子1″，2″，5″和6″发生共振，这可能是由于Rh-N键旋转受限所致。烯烃和脂族质子将彼此交换并且还与中间物质交换。交换机制可以被可视化为涉及Rh-N键断裂，T形（三坐标）中间物种的cod配体旋转，然后再复合。替代机理可以是在烯烃位置5”和6”处的Rh-cod键断裂。 T配合物的异构化，使得5''/ 6''向后移动至X，再加上杂环绕Rh-N键旋转（由于中间体的配位数减少而更容易），然后再进行1'配位'/ 2''转换为N，然后重新复合。一维H-1，C-13和2D NMR光谱中来自中间物种的NMR信号支持质子的交换。

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