Stable GaX2, InX2 and TlX2 radicals.
Stable GaX2, InX2 and TlX2 radicals.
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DOI：
10.1038/nchem.1870
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发表时间：
2014-04
期刊：
影响因子：
21.8
通讯作者：
A. Protchenko;Deepak Dange;J. Harmer;C. Tang;Andrew D. Schwarz;M. Kelly;N. Phillips;R. Tirfoin;K. H. Birjkumar;Cameron Jones;N. Kaltsoyannis;P. Mountford;S. Aldridge
中科院分区：
文献类型：
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作者：
A. Protchenko;Deepak Dange;J. Harmer;C. Tang;Andrew D. Schwarz;M. Kelly;N. Phillips;R. Tirfoin;K. H. Birjkumar;Cameron Jones;N. Kaltsoyannis;P. Mountford;S. Aldridge
第13族金属的化学性质由+1和+3氧化态主导，并且简单的单体M（II）物质通常是短寿命的高反应性物质。在这里，我们报告了第一个热稳定的单体MX2自由基的镓，铟和铊。通过利用空间要求高的硼基取代基，可以合成M（II）（硼基）2（M = Ga、In、Tl）类型的化合物。这些在130 °C以上分解，并通过X射线晶体学进行固态结构表征。电子顺磁共振和计算研究揭示了所有三种自由基的主要金属中心特征（>70%的金属自旋密度）。M（II）物种已被调用作为关键的短暂的中间体在众所周知的电子转移过程中，一贯的，这些新的孤立物种的化学行为揭示了在金属中心的轻便的单电子穿梭过程。
The chemistry of the Group 13 metals is dominated by the +1 and +3 oxidation states, and simple monomeric M(II)species are typically short-lived, highly reactive species. Here we report the first thermally robust monomeric MX2radicals of gallium, indium and thallium. By making use of sterically demanding boryl substituents, compounds of the type M(II)(boryl)2(M = Ga, In, Tl) can be synthesized. These decompose above 130 °C and are amenable to structural characterization in the solid state by X-ray crystallography. Electron paramagnetic resonance and computational studies reveal a dominant metal-centred character for all three radicals (>70% spin density at the metal). M(II)species have been invoked as key short-lived intermediates in well-known electron-transfer processes; consistently, the chemical behaviour of these novel isolated species reveals facile one-electron shuttling processes at the metal centre.