An Isolable Phosphaethynolatoborane and Its Reactivity
An Isolable Phosphaethynolatoborane and Its Reactivity
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DOI：
10.1002/anie.201712624
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发表时间：
2018-02-19
影响因子：
16.6
通讯作者：
Goicoechea, Jose M.
中科院分区：
文献类型：
--
作者：
Wilson, Daniel W. N.;Hinz, Alexander;Goicoechea, Jose M.
研究了稳定的磷酸乙酯硼烷[B]OCP （1, [B]=N，N-二（2,6-二异丙基苯基）-2,3-二氢- 1h -1,3,2-二氮硼基）的合成和表征。在一系列的反应性研究中探讨了1中P-C键相对于自由离子（PCO-）增加的三键特性。化合物1在给体溶剂中容易二聚形成环状五元6-芳香化合物，环- p -2{C[B]}O{CO[B]}(2)，该化合物在紫外线照射下脱碳。相比之下，镍介导的1二聚化反应产生了二磷酸环丁烯[P(CO[B])](2)。当1与有机锂试剂MesLi （Mes=2,4,6-三甲基苯基）反应时，观察到硼基部分移位，形成石基-硼基-磷酸烯烃[LiOC[B]P(Mes)](2)。还描述了该物质对亲电试剂的反应性。
The synthesis and characterization of a stable phosphaethynolatoborane, [B]OCP (1, [B]=N,N-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), is described. The increased triple bond character of the P-C bond in 1 relative to the free ion (PCO-) is probed in a series of reactivity studies. Compound 1 readily dimerises in donor solvents to afford a cyclic five-membered 6-aromatic compound, cyclo-P-2{C[B]}O{CO[B]} (2), which decarbonylates on UV irradiation. By contrast the nickel-mediated dimerisation of 1 affords the isomeric diphosphacyclobutene [P(CO[B])](2). When 1 is reacted with organolithium reagents such as MesLi (Mes=2,4,6-trimethylphenyl), the boryl moiety shifts and the formation of the lithoxy-boryl-phosphaalkene [LiOC[B]P(Mes)](2) was observed. The reactivity of this species towards electrophiles is also described.