metalation of primary or cyclic diphosphanylsiloxane compounds and subsequent oxidative coupling using C2H4Br2 as reagent. Starting from the cyclic diphosphanylsiloxane [O(iPr2Si)2PH]2, the reaction with the silazanides of the earth alkaline metals leads to the metalated compounds [M(DME)2O(iPr2Si)2P}2] (1: M = Ca, 2: M = Sr, 3: M = Ba). Subsequent oxidation yields the bicyclic species P2[O(iPr2Si)2]2
硅氧烷桥接的 P2 和 P4 化合物的合成可以通过伯或环状二膦基硅氧烷化合物的金属化和随后使用 C2H4Br2 作为试剂的氧化偶联来实现。从环状二膦基硅氧烷 [O(iPr2Si)2PH]2 开始,与碱土金属的硅氮化物反应生成金属化化合物 [M(DME)2O(iPr2Si)2P}2] (1: M = Ca , 2: M = Sr, 3: M = Ba)。随后的氧化产生双环物质 P2[O(iPr2Si)2]2 (4)。在与伯二膦基硅氧烷 O(iPr2Si)2PH2 的类似反应序列中,可以获得环状二膦 O(iPr2SiPH)2 (5) 并成功用于相同的反应途径,导致相应的金属化化合物 6。进一步氧化偶联导致在分子间 P-P 键形成中,
Hybrid Cage Compounds with Organic and Inorganic Building Blocks
作者:Andreas Kracke、Carsten von Hänisch、Nina Kramer
DOI:10.1002/ejic.201200384
日期:2012.6
Two new hybrid ligands that exhibit organic as well as siloxane chains between four phosphorus atoms in bridge-head positions were synthesized. These species show a very different ability with regard to the formation of coordination compounds. Whereas compound 1 with the short (C2H4)2O ether units shows no ability to act as a ligand, the compound with the longer (C2H4O)2C2H4 chains between the siloxane