Department of Chemistry and the Center for Computational Chemistry, The University of Georgia , Athens, Georgia 30602-2556, United States.
J Am Chem Soc. 2017 May 24;139(20):6859-6862. doi: 10.1021/jacs.7b03794. Epub 2017 May 12.
Sulfurization of anionic N-heterocyclic dicarbene, [:C{[N(2,6-PrCH)]CHCLi}] (2), with elemental sulfur (in a 1:2 ratio) in EtO at low temperature gives 3 by inserting two sulfur atoms into the Li-C (i.e., C2 and C4) bonds in polymeric 2. Further reaction of 3 with 2 equiv of elemental sulfur in THF affords 4 via unexpected C-H bond activation, which represents the first anionic dithiolene radical to be structurally characterized in the solid state. Alternatively, 4 may also be synthesized directly by reaction of 1 with sulfur (in a 1:4 ratio) in THF. Reaction of 4 with GeCl·dioxane gives an anionic germanium(IV)-bis(dithiolene) complex (5). The nature of the bonding in 4 and 5 was probed by experimental and theoretical methods.
阴离子型 N-杂环二碳烯（[:C{[N(2,6-PrCH)]CHCLi}]，2）与元素硫（1:2 摩尔比）在 EtO 中于低温下反应，通过将两个硫原子插入聚合物 2 的 Li-C（即 C2 和 C4）键中，生成 3。3 与 2 当量的元素硫在 THF 中进一步反应，通过意外的 C-H 键活化生成 4，这代表了第一个在固态下结构得到确证的阴离子二硫烯自由基。或者，4 也可以通过 1 与硫（1:4 摩尔比）在 THF 中直接反应合成。4 与 GeCl·dioxane 的反应生成阴离子型锗（IV）-双（二硫烯）配合物（5）。通过实验和理论方法研究了 4 和 5 的成键性质。
