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首页> 外文期刊>Chemistry: A European journal >Synthesis of planar chiral iridacycles by cationic metal π-coordination: Facial selectivity, and conformational and stereochemical consequences
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Synthesis of planar chiral iridacycles by cationic metal π-coordination: Facial selectivity, and conformational and stereochemical consequences

机译：阳离子金属π-配位合成平面手性iridacycles：面部选择性以及构象和立体化学的后果

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摘要

Facial selectivity during the π-coordination of pseudo-tetrahedral iridacycles by neutral (Cr(CO) _3), monocationic (Cp*Ru ~+), and biscationic (Cp*Ir ~(2+)) metal centers was directly influenced by the coulombic imbalance in the coordination sphere of the chelated Ir center. We also showed by using theoretical calculations that the feasibility of the related metallacycles that displayed metallocenic planar chirality was dependent to the presence of an electron-donating group, such as NMe _2, which contributed to the overall stability of the complexes. When the π-bonded moiety was the strongly electron-withdrawing Cp*Ir ~(2+) group, the electron donation from NMe _2 resulted in major conformational changes, with a barrier to rotation of about 17 kcal mol ~(-1) for this group that became spectroscopically diastereotopic (high-field ~1H NMR spectroscopy). This peculiar property is proposed as a means to introduce a new type of constitutional chirality at the nitrogen center: planar chirality at tertiary aromatic amines.
机译：中性（Cr（CO）_3），单阳离子性（Cp * Ru〜+）和双阳离子性（Cp * Ir〜（2+））金属中心在π-配准拟四面体iridacycles的过程中的面部选择性直接受到金属离子的影响。螯合的Ir中心配位范围内的库仑不平衡。我们还通过使用理论计算表明，显示金属茂金属平面手性的相关金属环的可行性取决于给电子基团（例如NMe _2）的存在，这有助于配合物的整体稳定性。当π键部分是强吸电子Cp * Ir〜（2+）基团时，NMe _2的电子给体导致主要构象变化，约17 kcal mol〜（-1）的旋转势垒该组在光谱上变为非对映体（高场〜1H NMR光谱）。提出了这种独特的性质，作为在氮中心引入新型结构手性的方法：在叔芳族胺上的平面手性。

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