一种稠环1,4-二锑苯双自由基类似物的分离。
Isolation of an Annulated 1,4-Distibabenzene Diradicaloid.
作者信息
Steffenfauseweh Henric, Rottschäfer Dennis, Vishnevskiy Yury V, Neumann Beate, Stammler Hans-Georg, Szczepanik Dariusz W, 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.
Current address: Department of Chemistry, Philipps-University Marburg, Hans-Meerwein-Str. 4, Marburg, Germany.
出版信息
Angew Chem Int Ed Engl. 2023 May 2;62(19):e202216003. doi: 10.1002/anie.202216003. Epub 2023 Jan 31.
The first 1,4-distibabenzene-1,4-diide compound [(ADC)Sb] (5) based on an anionic dicarbene (ADC) (ADC=PhC{N(Dipp)C} , Dipp=2,6-iPr C H ) is reported as a bordeaux-red solid. Compound 5, featuring a central six-membered C Sb ring with formally Sb atoms may be regarded as a base-stabilized cyclic bis-stibinidene in which each of the Sb atoms bears two lone-pairs of electrons. 5 undergoes 2 e-oxidation with Ph C[B(C F ) ] to afford [(ADC)Sb] [B(C F ) ] (6) as a brick-red solid. Each of the Sb atoms of 6 has an unpaired electron and a lone-pair. The broken-symmetry open-shell singlet diradical solution for (6) is calculated to be 2.13 kcal mol more stable than the closed-shell singlet. The diradical character of (6) according to SS-CASSCF (state-specific complete active space self-consistent field) and UHF (unrestricted Hartree-Fock) methods amounts to 36 % and 39 %, respectively. Treatments of 6 with (PhE) yield [(ADC)Sb(EPh)] [B(C F ) ] (7-E) (E=S or Se). Reaction of 5 with (cod)Mo(CO) affords [(ADC)Sb] Mo(CO) (8).
报道了首例基于阴离子型二碳烯（ADC）（ADC = PhC{N(Dipp)C} ，Dipp = 2,6-iPr₂C₆H₃）的1,4-二锑苯-1,4-二亚胺化合物[(ADC)Sb] (5)，它是一种酒红色固体。化合物5具有一个中心六元C₂Sb环，其中的Sb原子形式上带有形式电荷，可被视为一种碱稳定的环状双亚锑烯，其中每个Sb原子带有两对孤对电子。5与Ph₃C[B(C₆F₅)₄]发生2e⁻氧化反应，生成砖红色固体[(ADC)Sb]⁺[B(C₆F₅)₄]⁻ (6)。6中的每个Sb原子都有一个未成对电子和一对孤对电子。计算得出，(6)的破缺对称性开壳单重态双自由基溶液比闭壳单重态稳定2.13 kcal·mol⁻¹。根据SS-CASSCF（态特异性完全活性空间自洽场）和UHF（非限制Hartree-Fock）方法，(6)的双自由基特征分别为36%和39%。用(PhE)处理6得到[(ADC)Sb(EPh)]⁺[B(C₆F₅)₄]⁻ (7-E)（E = S或Se）。5与(cod)Mo(CO)₄反应生成[(ADC)Sb]₂Mo(CO)₄ (8)。
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