Conformation of tripod Metal Templates in CH3C(CH2PPh2)3MLn (n = 2, 3): Neural Networks in Conformational Analysis†
Conformation of tripod Metal Templates in CH3C(CH2PPh2)3MLn (n = 2, 3): Neural Networks in Conformational Analysis†
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CH3C(CH2PPh2)3MLn (n = 2, 3) 中三脚架金属模板的构象：构象分析中的神经网络†
DOI：
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发表时间：
1996
期刊：
影响因子：
--
通讯作者：
L. Zsolnai
中科院分区：
文献类型：
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作者：
Stefan Beyreuther;J. Hunger;G. Huttner;S. Mann;L. Zsolnai
基于化合物tripodCoL2和tripodCoL3中82个tripodCo模板的固态结构，分析了三脚金属模板CH3C(CH2Ph2)3M跨越的构象空间。系统分析，包括构象空间群散点图、主成分分析和偏最小二乘技术，揭示了一系列基本规律：苯基的扭转与螯合笼的双环辛烷型框架的扭转倾斜密切相关。对于这种偏斜的一种意义，存在两类低能构象，它们的不同之处在于苯基排列的螺旋度和螯合物主链中的扭转偏斜程度。从散点图可以明显看出，螺旋度的变化可能通过一环或两环翻转机制发生。通过神经网络方法对相同数据的分析也可以明显看出上述方法发现的基本规律。事实上，无论配体 L 和晶体环境如何，在 tripodCoL2 和 tripodCoL3 中都发现了这些规律，这意味着三脚金属模板的构象是由作用在它们内部的力决定的，而不是由它们各自的化学或晶体环境施加在它们上的力决定的。结果表明，尽管这些分类源自仅包含钴化合物的数据基础，但无论涉及哪种特定金属，都是三脚架金属模板的特征。
The conformational space spanned by tripod metal templates CH3C(CH2Ph2)3M is analysed on the basis of the solid-state structures of 82 tripodCo templates in compounds tripodCoL2 and tripodCoL3. Systematic analysis, including the techniques of conformational space group scatter graphs, principal-component analysis, and partial least squares, reveals a series of basic regularities: The torsion of the phenyl groups is strongly linked to the torsional skew of the bicyclooctane-type framework of the chelate cage. For one sense of this skew there are two classes of low-energy conformation that differ by the helicity of the phenyl arrangement and by the degree of torsional skew in the chelate backbone. From the scatter graphs it is evident that a change in helicity may occur by one- or by two-ring flip mechanisms. The basic regularities found by the above methods are also evident from the analysis of the same data by a neural network approach. The fact that these regularities are found for tripodCoL2 and tripodCoL3, irrespective of the widely different coligands L and crystal environments, means that the conformation of the tripod metal templates is governed by the forces acting within them and not so much by the forces imposed on them by their individual chemical or crystal environment. It is shown that the classifications, although derived from a data basis only containing Co compounds, are characteristic for tripod metal templates irrespective of the specific metal involved.
影响因子：
5.6
作者：
KNELLER, DG;COHEN, FE;LANGRIDGE, R
通讯作者：
LANGRIDGE, R