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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and dynamic behaviour of zwitterionic [M(η~6-C_6H_5-BPh_3)(coe)_2] (M = Rh, Ir) cyclooctene complexes
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Synthesis and dynamic behaviour of zwitterionic [M(η~6-C_6H_5-BPh_3)(coe)_2] (M = Rh, Ir) cyclooctene complexes

机译：两性离子[M（η〜6-C_6H_5-BPh_3）（coe）_2]（M = Rh，Ir）环辛烯配合物的合成和动力学行为

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摘要

The synthesis and structural characterization of zwitterionic [(η~6-C_6H_5-BPh_3)M(coe)_2] (M = Rh, Ir) cyclooctene complexes is described. Both complexes exhibit an unusual exo–endo conformation of both cyclooctene ligands in the solid state. However, an equilibrium between the endo–endo and exo–endo rotational isomers arising from the hindered rotation about the metal–cyclooctene bond is observed in solution. Rotational barriers of around 65 kJ mol~(?1) (Rh) and 84 kJ mol~(?1) (Ir) have been determined by 2D EXSY NMR spectroscopy. The rotation process has also been studied by DFT calculations that showed that the dynamic behaviour is a consequence of the oscillation of the cyclooctene ligands about the metal–olefin bond instead of completing a full rotation.
机译：描述了两性离子[（η〜6-C_6H_5-BPh_3）M（coe）_2]（M = Rh，Ir）环辛烯配合物的合成和结构表征。两种配合物均表现出固态的两种环辛烯配体具有不同寻常的外-内构象。但是，在溶液中观察到了由于绕金属-环辛烯键旋转受阻而引起的内-内-外-内-外旋转异构体之间的平衡。通过2D EXSY NMR光谱确定了约65 kJ mol〜（？1）（Rh）和84 kJ mol〜（？1）（Ir）的旋转势垒。还通过DFT计算研究了旋转过程，结果表明动力学行为是环辛烯配体围绕金属-烯烃键振动而不是完全旋转的结果。

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