A Complete Triad of Zero‐Valent 17‐Electron Monoradicals of Group 7 Elements Stabilized by m ‐Terphenyl Isocyanides
A Complete Triad of Zero‐Valent 17‐Electron Monoradicals of Group 7 Elements Stabilized by m ‐Terphenyl Isocyanides
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间·三联苯异氰化物稳定的第 7 族元素的完整零价 17 价电子单价基团
DOI：
10.1002/anie.202300254
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Abram, Ulrich
中科院分区：
文献类型：
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作者：
Salsi, Federico;Wang, Shuai;Teutloff, Christian;Busse, Marvin;Neville, Michael L.;Hagenbach, Adelheid;Bittl, Robert;Figueroa, Joshua S.;Abram, Ulrich
首次以晶体形式分离出三个第7族元素的单核17电子络合物系列，并用X-射线衍射和光谱方法进行了研究。顺磁性化合物的组成为[M0(CO)(CNP-F-ArDArF2)4](M=Mn，TC，Re；ArDArF2=2，6-(3，5-(CF3)2C6H3)2C6H2F)，并由四个空间封闭的异氰化物稳定，防止金属化合物二聚。它们具有以羰基配体为顶端的方形金字塔结构。Re和Tm化合物的冷冻溶液EPR谱具有明显的各向异性，其中一个组分具有较大的99Tc超精细相互作用和185,187Re超精细作用。用高场EPR(Q带和W带)研究了锰(0)络合物的EPR参数。
The first consistent series of mononuclear 17‐electron complexes of three Group 7 elements has been isolated in crystalline form and studied by X‐ray diffraction and spectroscopic methods. The paramagnetic compounds have a composition of [M0(CO)(CNp‐F‐ArDArF2)4] (M=Mn, Tc, Re; ArDArF2=2,6‐(3,5‐(CF3)2C6H3)2C6H2F) and are stabilized by four sterically encumbering isocyanides, which prevent the metalloradicals from dimerization. They have a square pyramidal structure with the carbonyl ligands as apexes. The frozen‐solution EPR spectra of the rhenium and technetium compounds are clearly anisotropic with large99Tc and185,187Re hyperfine interactions for one component. High‐field EPR (Q band and W band) has been applied for the elucidation of the EPR parameters of the manganese(0) complex.