Forging Ru–C sp2 Bonds in Paddlewheel Complexes Using the Lithium–Halogen Exchange Reaction
Forging Ru–C sp2 Bonds in Paddlewheel Complexes Using the Lithium–Halogen Exchange Reaction
复制标题
利用锂-卤素交换反应在桨轮配合物中锻造 Ru-C sp2 键
DOI：
10.1021/acs.inorgchem.8b03216
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发表时间：
2019
影响因子：
4.6
通讯作者：
Ren, Tong
中科院分区：
文献类型：
--
作者：
Raghavan, Adharsh;Mash, Brandon L.;Ren, Tong
本文报道了在桨轮二钌物质中形成 Ru-Csp2 键的第一个例子。通过与多种对位取代芳基卤化物进行锂-卤素交换反应，合成了一系列六种Ru2(ap)4(C6H4-4-X)型化合物（ap= 2-苯胺基吡啶酯；X = NMe2(1),N,N-(C6H4-4-OMe)2(2),tBu (3), H (4), Br (5), CF3(6)）。这些化合物已通过电子吸收光谱、循环伏安法、质谱和磁性研究进行了表征，并通过单晶 X 射线衍射研究确定了它们的分子结构。所有化合物均处于Ru25+氧化态，基态电子构型为σ2π4δ2(π*δ*)3。 1-6 的晶体结构证实了这一点，表明 Ru-Ru 键级为 2.5。电化学数据表明，σ-芳基是比σ-炔基更强的供体。一系列电子上不同的取代基可以更仔细地检查二钌叶轮核和轴向芳基配体上的电子共轭程度。
Reported herein are the first examples of the formation of Ru–Csp2bonds in paddlewheel diruthenium species. A series of six Ru2(ap)4(C6H4-4-X) type compounds (ap= 2-anilinopyridinate; X = NMe2(1),N,N-(C6H4-4-OMe)2(2),tBu (3), H (4), Br (5), CF3(6)) was synthesized by employing the lithium–halogen exchange reaction with a variety of para-substituted aryl halides. These compounds have been characterized via electronic absorption spectroscopy, cyclic voltammetry, mass spectrometry, and magnetism studies, and their molecular structures have been established by single-crystal X-ray diffraction studies. All compounds are in the Ru25+oxidation state, with a ground-state electronic configuration of σ2π4δ2(π*δ*)3. Crystal structures of1–6confirm this, indicating a Ru–Ru bond order of 2.5. Electrochemical data suggest that the σ-aryls are stronger donors than the σ-alkynyls. A range of electronically different substituents allows for a closer inspection of the extent of electronic conjugation across the diruthenium paddlewheel core and the axial aryl ligand.