A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques.
A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques.
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DOI：
10.1002/anie.201511269
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发表时间：
2016-03-07
期刊：
影响因子：
--
通讯作者：
Macgregor SA
中科院分区：
文献类型：
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作者：
Chadwick FM;Rees NH;Weller AS;Krämer T;Iannuzzi M;Macgregor SA
在前驱体1,3 -戊二烯配合物中加入H2，通过固气单晶转变合成了戊烷σ -配合物[Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][barf4]。通过低温单晶X射线衍射（150 K）和SSNMR光谱（158 K）表征，揭示了在线性烷烃的2,4位上通过两个Rh⋅⋅⋅H−C相互作用进行配位。固态结构的周期性DFT计算和分子动力学提供了对实验观察到的Rh⋅⋅⋅H−C相互作用、晶格中的扩展环境和SSNMR数据所涉及的温度依赖性戊烷重排的深入了解。
The pentane σ‐complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF 4] is synthesized by a solid/gas single‐crystal to single‐crystal transformation by addition of H2 to a precursor 1,3‐pentadiene complex. Characterization by low temperature single‐crystal X‐ray diffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination through two Rh⋅⋅⋅H−C interactions in the 2,4‐positions of the linear alkane. Periodic DFT calculations and molecular dynamics on the structure in the solid state provide insight into the experimentally observed Rh⋅⋅⋅H−C interaction, the extended environment in the crystal lattice and a temperature‐dependent pentane rearrangement implicated by the SSNMR data.