Inter- versus Intramolecular Structural Manipulation of a Dichromium(II) Pacman Complex through Pressure Variation

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• 作者：Charlotte J. Stevens ; Alessandro Prescimone ; Floriana Tuna ; Eric J. L. McInnes ; Simon Parsons ; Carole A. Morrison ; Polly L. Arnold ; Jason B. Love
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：January 4, 2016
• 年：2016
• 卷：55
• 期：1
• 页码：214-220
• 全文大小：404K
• ISSN：1520-510X

文摘

The effect of pressure on the intranuclear M···M separation and intermolecular secondary interactions in the dinuclear chromium Pacman complex [Cr₂(L)](C₆H₆) was evaluated because this compound contains both a short Cr···Cr separation and an exogenously bound molecule of benzene in the solid state. The electronic structure of [Cr₂(L)] was determined by electron paramagnetic resonance spectroscopy, SQUID magnetometry, and density functional theory calculations and shows a diamagnetic ground state through antiferromagnetic exchange, with no evidence for a Cr–Cr bond. Analysis of the solid-state structures of [Cr₂(L)](C₆H₆) at pressures varying from ambient to 3.0 GPa shows little deformation in the Cr···Cr separation, i.e., no Cr–Cr bond formation, but instead a significantly increased interaction between the exogenous arene and the chromium iminopyrrolide environment. It is therefore apparent from this analysis that [Cr₂(L)] would be best exploited as a rigid chemical synthon, with pressure regulation being used to mediate the approach and secondary interactions of possible substrates.