一种开壳层单重态锡双自由基与氢分裂
An Open-Shell Singlet Sn Diradical and H Splitting.
作者信息
Sharma Mahendra K, Rottschäfer Dennis, Glodde Timo, Neumann Beate, Stammler Hans-Georg, Ghadwal Rajendra S
机构信息
Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, 33615, Bielefeld, Germany.
出版信息
Angew Chem Int Ed Engl. 2021 Mar 15;60(12):6414-6418. doi: 10.1002/anie.202017078. Epub 2021 Feb 5.
The first Sn diradical [(ADC )Sn] (4) based on an anionic dicarbene (ADC ={CN(Dipp)} CPh; Dipp=2,6-iPr C H ) scaffold has been isolated as a green crystalline solid by KC reduction of the corresponding bis-chlorostannylene [(ADC )SnCl] (3). The six-membered C Sn -ring of 4 containing six π-electrons shows a diatropic ring current, thus 4 may also be regarded as the first 1,4-distannabenzene derivative. DFT calculations suggest an open-shell singlet (OS) ground state of 4 with a remarkably small singlet-triplet energy gap (ΔE =4.4 kcal mol ), which is consistent with CASSCF (ΔE =6.6 kcal mol and diradical character y=37 %) calculations. The diradical 4 splits H at room temperature to yield the bis-hydridostannylene [(ADC )SnH] (5). Further reactivity of 4 has been studied with PhSeSePh and MeOTf.
首个基于阴离子型二卡宾（ADC ={CN(Dipp)}₂CPh；Dipp = 2,6 - iPr₂C₆H₃）骨架的锡双自由基[(ADC )₂Sn] (4) 通过相应的双氯亚锡烯[(ADC )₂SnCl] (3) 的KC还原反应被分离出来，呈绿色晶体状固体。4的六元C₂Sn₂环含有六个π电子，显示出抗磁环流，因此4也可被视为首个1,4 - 二锡苯衍生物。密度泛函理论（DFT）计算表明4的基态为开壳层单重态（OS），单重态 - 三重态能隙（ΔE = 4.4 kcal·mol⁻¹）非常小，这与完全活性空间自洽场（CASSCF）计算结果（ΔE = 6.6 kcal·mol⁻¹，双自由基特征y = 37%）一致。双自由基4在室温下能使H₂分裂，生成双氢化亚锡烯[(ADC )₂SnH₂] (5)。还研究了4与PhSeSePh和MeOTf的进一步反应活性。
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