σ-π Continuum in Indole-Palladium(II) Complexes.
σ-π Continuum in Indole-Palladium(II) Complexes.
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DOI：
10.1002/anie.201601992
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发表时间：
2016-04
影响因子：
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通讯作者：
Koji Yamamoto;S. Kimura;Tetsuro Murahashi
中科院分区：
文献类型：
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作者：
Koji Yamamoto;S. Kimura;Tetsuro Murahashi
(杂芳烃)-金属相互作用的内在特征一直难以捉摸，主要是因为非锚定的杂芳烃-金属络合物的不稳定性质阻碍了系统的结构分析。我们报道了一系列非锚定的吲哚-钯(II)配合物的成功分离和系统结构分析。结果表明，吲哚与金属的相互作用存在σ-π连续体，并考虑到吲哚具有较强的给电子能力，认为吲哚与金属中心的配位方式主要是惠兰中间型σ方式。讨论了影响吲哚-金属相互作用σ-或π-性质的几个因素。
The intrinsic features of (hetero-arene)-metal interactions have been elusive mainly because the systematic structure analysis of non-anchored hetero-arene-metal complexes has been hampered by their labile nature. We report successful isolation and systematic structure analysis of a series of non-anchored indole-palladium(II) complexes. It was revealed that there is a σ-π continuum for the indole-metal interaction, while it has been thought that the dominant coordination mode of indole to a metal center is the Wheland-intermediate-type σ-mode in light of the seemingly strong electron-donating ability of indole. Several factors which affect the σ- or π-character of indole-metal interactions are discussed.