Synthesis, Structure, and Reactivity of Magnesium Pentalenides,Inorganic Chemistry

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Synthesis, Structure, and Reactivity of Magnesium Pentalenides
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2023-09-15 , DOI: 10.1021/acs.inorgchem.3c02087
Hugh J Sanderson ₁ , Gabriele Kociok-Köhn ₂ , Ulrich Hintermair _{1,

3}

Affiliation

The first magnesium pentalenide complexes have been synthesized via deprotonative metalation of 1,3,4,6-tetraphenyldihydropentalene (Ph₄PnH₂) with magnesium alkyls. Both the nature of the metalating agent and the reaction solvent influenced the structure of the resulting complexes, and an equilibrium between Mg[Ph₄Pn] and [ⁿBuMg]₂[Ph₄Pn] was found to exist and investigated by NMR, XRD, and UV–vis spectroscopic techniques. Studies on the reactivity of Mg[Ph₄Pn] with water, methyl iodide, and trimethylsilylchloride revealed that the [Ph₄Pn]^2– unit undergoes electrophilic addition at 1,5-positions instead of 1,4-positions known for the unsubstituted pentalenide, Pn^2–, highlighting the electronic influence of the four aryl substituents on the pentalenide core. The ratio of syn/anti addition was found to be dependent on the size of the incoming electrophile, with methylation yielding a 60:40 mixture, while silylation yielded exclusively the anti-isomer.

中文翻译：

五烯化镁的合成、结构和反应性

第一个五烯化镁配合物是通过1,3,4,6-四苯基二氢戊二烯 ( Ph ₄ PnH ₂ ) 与烷基镁的去质子金属化合成的。金属化剂和反应溶剂的性质都会影响所得配合物的结构，并且发现Mg[Ph ₄ Pn]和[ ⁿ BuMg] ₂ [Ph ₄ Pn]之间存在平衡，并通过NMR、XRD进行了研究和紫外可见光谱技术。对Mg[Ph ₄ Pn]与水、碘甲烷和三甲基氯硅烷的反应性的研究表明， [Ph ₄ Pn] ^{2 –}单元在 1,5 位而不是已知未取代的 1,4 位进行亲电加成pentalenide，Pn ^{2 –}，突出了四个芳基取代基对pentalenide核心的电子影响。发现顺式/反式加成的比例取决于引入的亲电子试剂的大小，甲基化产生60:40的混合物，而甲硅烷基化仅产生反式异构体。

更新日期：2023-09-15

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