芳烃稳定的η-五甲基环戊二烯基砷二价阳离子[(η-Cp*)As(甲苯)]
The Arene-Stabilized η -Pentamethylcyclopentadienyl Arsenic Dication [(η -Cp*)As(toluene)].
作者信息
Zhou Jiliang, Liu Liu Leo, Cao Levy L, Stephan Douglas W
机构信息
Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S3H6, Canada.
出版信息
Angew Chem Int Ed Engl. 2019 Apr 8;58(16):5407-5412. doi: 10.1002/anie.201902039. Epub 2019 Mar 18.
Double chloride abstraction of CpAsCl gives the dicationic arsenic species [(η -Cp)As(tol)][B(C F ) ] (2) (tol=toluene). This species is shown to exhibit Lewis super acidity by the Gutmann-Beckett test and by fluoride abstraction from [NBu ][SbF ]. Species 2 participates in the FLP activation of THF affording [(η -Cp*)AsO(CH ) (THF)][B(C F ) ] (5). The reaction of 2 with PMe or dppe generates [(Me P) As][B(C F ) ] (6) and [(σ-Cp*)PMe ][B(C F ) ] (7), or [(dppe)As][B(C F ) ] (8) and [(dppe)(σ-Cp*) ][B(C F ) ] (9), respectively, through a facile cleavage of C-As bonds, thus showcasing unusual reactivity of this unique As-containing compound.
对CpAsCl进行双氯化物提取得到双阳离子砷物种[(η -Cp)As(tol)][B(CF)] (2)（tol = 甲苯）。通过古特曼-贝克特测试以及从[NBu][SbF]中提取氟化物，表明该物种具有路易斯超强酸性。物种2参与了四氢呋喃（THF）的FLP活化反应，生成[(η -Cp*)AsO(CH)(THF)][B(CF)] (5)。2与PMe或dppe反应分别通过C-As键的轻易断裂生成[(MeP)As][B(CF)] (6)和[(σ-Cp*)PMe][B(CF)] (7)，或者[(dppe)As][B(CF)] (8)和[(dppe)(σ-Cp*)][B(CF)] (9)，从而展示了这种独特含砷化合物的异常反应性。
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