Nature of the Short Rh–Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH 2 CMe 2 CH 2 CH═CH 2 ) 2 ] −
Nature of the Short Rh–Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH 2 CMe 2 CH 2 CH═CH 2 ) 2 ] −
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短 Rh-Li 的性质 锂与铑 α-烯基配合物 [Rh(CH 2 CMe 2 CH 2 CH-CH 2 ) 2 ] 之间的接触
DOI：
10.1021/acs.inorgchem.1c00737
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发表时间：
2021
影响因子：
4.6
通讯作者：
Girolami, Gregory S.
中科院分区：
文献类型：
--
作者：
Liu, Sumeng;Smith, Brett A.;Kirkland, Justin K.;Vogiatzis, Konstantinos D.;Girolami, Gregory S.
本文报道了顺式-双（η1，η2- 2，2-二甲基-4-烯-1-基）铑酸根阴离子cis-[Rh（CH 2CMe 2CH 2CH <$CH2）2]−的制备及其在溶液和固体中与Li+的相互作用。对于锂（乙醚）盐[Li（Et 2 O）][Rh（CH 2CMe 2CH 2CH <$CH2）2]，在甲苯-d8中的VT-NMR和~ 1H {7 Li} NOE NMR研究表明，Li ~+离子与铑的dz ~ 2轨道非常接近。在锂（12-冠-4）盐[Li（12-冠-4）2][Li{Rh（CH 2CMe 2CH 2CH <$CH2）2}2]的固态结构中，一个锂原子被两个[Rh（CH 2CMe 2CH 2CH <$CH2）2]−阴离子包围，在这个组合中有两个异常短的Rh-Li距离，为2.48 <$。DFT计算、自然能量分解和ETS-NOCV分析表明，Rh中心的4dz 2轨道与Li+的2 pz轨道之间存在弱的配位相互作用. Rh和Li+之间的电荷转移项只贡献了总相互作用能的1/5，而化合物1和2中Rh和Li接近的主要驱动力是Li+被二烷基铑酸阴离子上的负电荷静电吸引.
We describe the preparation of thecis-bis(η1,η2-2,2-dimethylpent-4-en-1-yl)rhodate(I) anion,cis-[Rh(CH2CMe2CH2CH═CH2)2]−, and the interaction of this species with Li+both in solution and in the solid state. For the lithium(diethyl ether) salt [Li(Et2O)][Rh(CH2CMe2CH2CH═CH2)2], VT-NMR and1H{7Li} NOE NMR studies in toluene-d8show that the Li+cation is in close proximity to the dz2orbital of rhodium. In the solid-state structure of the lithium(12-crown-4) salt [Li(12-crown-4)2][Li{Rh(CH2CMe2CH2CH═CH2)2}2], one lithium atom is surrounded by two [Rh(CH2CMe2CH2CH═CH2)2]−anions, and in this assembly there are two unusually short Rh–Li distances of 2.48 Å. DFT calculations, natural energy decomposition, and ETS-NOCV analysis suggest that there is a weak dative interaction between the 4dz2orbitals on the Rh centers and the 2pzorbital of the Li+cation. The charge-transfer term between Rh and Li+contributes only about the 1/5 of the total interaction energy, however, and the principal driving force for the proximity of Rh and Li in compounds1and2is that Li+is electrostatically attracted to negative charges on the dialkylrhodiate anions.