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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Substituent-controlled preference of carbonyl group-metal coordination in d8 metal complexes with non-symmetric pentadentate ligands. Structural and stereochemical aspects?
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Substituent-controlled preference of carbonyl group-metal coordination in d8 metal complexes with non-symmetric pentadentate ligands. Structural and stereochemical aspects?

机译：具有不对称五齿配体的d8金属配合物中羰基-金属配位的取代基受控偏好。结构和立体化学方面？

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摘要

Chirally switchable Ni(_(II)) and Pd(_(II)) complexes were synthesized and fully characterized by X-ray crystallography and additionally by spectroscopic means (NMR and MS). The syntheses and characterization of their ligands are also reported. It was found that control of the stereochemical preference between (S*,S*) and (S*,R*) diastereomers by substituent modification of the ligand sidearms was possible in the solid state with the preferred atomic coordinations of the sidearms consistent with expectations based on the electron-withdrawing properties of the substituent -o-CF_3 group. The dilemma arising in terms of assigning the absolute configuration descriptors resulting from selecting between strictly following only the covalent bonds of the ligand and disregarding the nature of the bonds altogether and thus bringing the coordinate bonds into consideration to determine the stereochemical priority sequence is hereby resolved by declaring that the latter option is to be preferred. The results obtained here provide a clear indication that sidearm substitution of the Ni(_(II)) and Pd(_(II)) complexes need not disturb macromolecular stereochemical arrangements leading to quasidiastereomeric relationships. This permits the design of molecular systems sensitive to external stimuli with predictable macromolecular structure.
机译：合成了手性可切换的Ni（_（II））和Pd（_（II））配合物，并通过X射线晶体学以及光谱方法（NMR和MS）进行了全面表征。还报道了其配体的合成和表征。发现在固态下可以通过配体侧臂的取代基修饰来控制（S *，S *）和（S *，R *）非对映异构体之间的立体化学偏好，且侧臂的优选原子配位与预期相符基于取代基-o-CF_3基团的吸电子性质。在分配绝对构型描述符方面出现的难题，是通过严格选择仅遵循配体的共价键与完全不考虑键的性质之间的关系而产生的，从而通过考虑配位键来确定立体化学优先级序列声明后一种选择是首选。此处获得的结果清楚地表明，Ni（_（II））和Pd（_（II））配合物的侧臂取代不必干扰导致拟对映异构关系的大分子立体化学排列。这允许设计对具有可预测的大分子结构的外部刺激敏感的分子系统。

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