The Unusual Structural Behavior of Heteroleptic Aryl Copper(I) Thiolato Molecules: Cis vs Trans Structures and London Dispersion Effects
The Unusual Structural Behavior of Heteroleptic Aryl Copper(I) Thiolato Molecules: Cis vs Trans Structures and London Dispersion Effects
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DOI：
10.1021/acs.organomet.2c00018
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发表时间：
2022-03
期刊：
影响因子：
2.8
通讯作者：
W. Zou;J. Fettinger;P. Vasko;P. Power
中科院分区：
文献类型：
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作者：
W. Zou;J. Fettinger;P. Vasko;P. Power
一系列式{Cu 2（SAr）Mes}2的杂配芳基硫醇合铜（I）配合物（Ar = C6H3- 2，6-（C6H2- 2，4，6-Me3）2（ArMe6），1; C6H3- 2，6-（C6H3- 2，6-iPr2）2（AriPr 4），2; C6H3- 2，6-（C6 H2 - 2，4，6-iPr 3）2（AriPr 6），3）和{Cu 4（SAr）Mes 3}通过均三甲苯铜（I）与相应的大体积三联苯硫醇反应并消除均三甲苯，合成了（Ar = C6 H-2，6-（C6 H2 - 2，4，6-iPr 3）2- 3，5-iPr 2（AriPr 8），4）。所有的配合物，其特征在于通过单晶X-射线衍射分析和光谱（NMR，红外，和UV-vis）。1 - 3的数据揭示了四金属Cu 4核结构，其中两个硫醇基或两个异亚丙基甲苯基配体桥接金属。尽管1和2具有预期的传统交替硫醇基和均三甲苯基桥接模式，3具有先前未知的结构排列，其中两个硫醇基配体彼此相邻。由于配合物3在硫醇配体上具有更拥挤的芳基，因此3中配体的顺式排列在空间上是违反直觉的，并且可能是由于伦敦色散（LD）能量效应。Complex 4还具有不寻常的结构模式，其中可能由于空间原因，结构中仅包含单个硫代配体。它具有一个平面梯形Cu 4核心，其中三个Cu-Cu边缘由mesityl基团桥接，而其余的Cu-Cu边缘由巯基配体桥接。色散关联密度泛函（DFT）计算表明，3具有最高的LD效应稳定性，这是由于异丙基配体取代基的C-H···H-C相互作用数目增加所致.
A series of heteroleptic aryl copper(I) thiolato complexes of formula {Cu2(SAr)Mes}2(Ar = C6H3-2,6-(C6H2-2,4,6-Me3)2(ArMe6),1; C6H3-2,6-(C6H3-2,6-iPr2)2(AriPr4),2; C6H3-2,6-(C6H2-2,4,6-iPr3)2(AriPr6),3) and {Cu4(SAr)Mes3} (Ar = C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2(AriPr8),4) were synthesized by the reactions of the corresponding bulky terphenyl thiols with mesitylcopper(I) with elimination of mesitylene. All complexes were characterized by single crystal X-ray diffraction analysis and spectroscopy (NMR, infrared, and UV–vis). The data for1–3revealed tetrametallic Cu4core structures in which two thiolato or two mesityl ligands bridge the metals. Although1and2feature the expected conventional alternating thiolato and mesityl bridging patterns,3has a previously unknown structural arrangement in which the two thiolato ligands are adjacent to each other. Since complex3has a more crowding aryl group on the thiolato ligands, the cis arrangement of the ligands in3is sterically counterintuitive and is likely due to London dispersion (LD) energy effects. Complex4also has an unusual structural pattern in which only a single thiolato ligand is incorporated in the structure probably for steric reasons. It has a planar trapezoidal Cu4core in which three Cu–Cu edges are bridged by the mesityl groups while the remaining Cu–Cu edge is thiolato ligand bridged. Dispersion connected DFT calculations show that3has the highest LD effect stabilization arising from the increased numbers of C–H···H–C interactions of the isopropyl ligand substituents.