Geometrically Enforced Donor-Facilitated Dehydrocoupling Leading to an Isolable Arsanylidine-Phosphorane
Geometrically Enforced Donor-Facilitated Dehydrocoupling Leading to an Isolable Arsanylidine-Phosphorane
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DOI：
10.1021/ja502625z
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发表时间：
2014-04-30
影响因子：
15
通讯作者：
Kilian, Petr
中科院分区：
文献类型：
--
作者：
Chalmers, Brian A.;Buehl, Michael;Kilian, Petr
一个接近的Lewis碱性基团促进了膦-砷的分子内温和的脱氢P-As偶联，提供了具有空间可及的两个配位的砷原子的热稳定性和水解性稳定的Arsanylidine-磷烷4。4的形成是热中和的，因为脱氢与给体配位是一致的。4与有限的氧气反应，通过形成环低聚精氨酸，显示出类似于阿西尼烯的反应活性，支持了4中碱稳定的阿西尼烯R3P->；ASR的成键公式。
A proximate Lewis basic group facilitates the mild dehydrogenative P-As intramolecular coupling in the phosphine-arsine peri-substituted acenaphthene 3, affording thermally and hydrolytically stable arsanylidine-phosphorane 4 with a sterically accessible two-coordinate arsenic atom. The formation of 4 is thermoneutral due to the dehydrogenation being concerted with the donor coordination. Reaction of 4 with a limited amount of oxygen reveals arsinidene-like reactivity via formation of cyclooligoarsines, supporting the formulation of the bonding in 4 as base-stabilized arsinidene R3P -> AsR.