Direct Access to <i>cis</i>-1,2-Dihydro-1,2-diphosphetes from Butadiynes and Terminal Phosphinidene Complexes
作者:Ngoc Hoa Tran Huy、Louis Ricard、François Mathey
DOI:10.1021/om970487t
日期:1997.9.1
Transient terminal phosphinidenecomplexes [RP→W(CO)5] (R = Ph, Me, Bz, allyl), as generated from the corresponding 7-phosphanorbornadiene complexes, react with substituted butadiynes to afford the corresponding 3-alkynyl-1,2-dihydro-1,2-diphosphete complexes by insertion of a second phosphinidene unit into the alkynyl-substituted P-C ring bond of the initially formed phosphirene complexes. According
suggest that terminal allylphosphinidene pentacarbonyltungsten complex 1 can evolve either by intramolecular P + C˭C cycloaddition or by [1,2] H C to P shift to give 2 or 6. Upon thermolysis of the 7-allyl-7-phosphanorbornadiene precursor, the transient complex 1 gives two diastereomeric dimers 4a,b derivingfrom a head-to-tail P + C˭C intermolecular cycloaddition and another dimer 5 derivingfrom the [4
摘要 DFT 计算表明末端烯丙基膦亚基五羰基钨配合物 1 可以通过分子内 P + C˭C 环加成或通过 [1,2] HC 向 P 转变生成 2 或 6。 7-烯丙基-7-膦降冰片二烯前体的热解,瞬态复合物 1 产生两个非对映体二聚体 4a,b,源自头对尾 P + C˭C 分子间环加成,另一个二聚体 5 源自 1 与 6 的 [4 + 1] 环加成,然后进行分子内氢膦化. 图形概要