2,4-DI-TERT-BUTYL-1-LAMBDA(3),3-LAMBDA(3)-DIPHOSPHININES - TARGETED SYNTHESIS AT IRON(0) CENTERS AND OXIDATIVE RELEASE
2,4-DI-TERT-BUTYL-1-LAMBDA(3),3-LAMBDA(3)-DIPHOSPHININES - TARGETED SYNTHESIS AT IRON(0) CENTERS AND OXIDATIVE RELEASE
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DOI：
10.1002/anie.199501981
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发表时间：
1995-02-03
期刊：
影响因子：
--
通讯作者：
ZENNECK, U
中科院分区：
文献类型：
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作者：
BOHM, D;KNOCH, F;ZENNECK, U
三价磷原子和CR片段是等电子的构建块，可以在许多有机磷化合物中占据同等位置，例如在杂芳烃中。这一族中最简单的成员d3-膦(磷苯)“]是已知的，以及它的许多取代产物。[‘]膦可以作为氧供体，利用磷上的唯一对，也可以作为环Q6配体。在三种可能的双膦异构体中，到目前为止，只有2，3，5，6-四(三氟甲基)-I_3，4I_3-二膦类似物在溶液中制备和光谱表征。特丁基磷杂乙炔lf41的一个环三聚产物被表征为一个x-键的三磷杂环烯。[~]1的第二个三聚产物被认为是一个配位的1，3，5-三膦杂菲；[~‘这一点尚未得到确凿的证明。[’]我们报道了一种在铁(O)的配位球面上通过[2+2+21]环加成两个磷杂膦和一个末端炔来有效地合成1-L3，3L3-二膦的方法。还讨论了这些LI3，3A3-双膦在氧化条件下的释放。
Trivalent phosphorus atoms and CR fragments are isoelectronic building blocks that can occupy equivalent positions in many organophosphorus compounds, for example in heteroarenes. The simplest member of this group, d3-phosphinine (phosphabenzene)"] is known, as well as many of its substitution products.['] Phosphinines can act as o-donor Ijgands, utilizing the lone pair on phosphorus, and also as cyclic q6 ligands.['] Of the three possible diphosphinine isomers, only 2, 3, 5, 6-tetrakis (trifluoromethy1)-I i3, 4i3-diphosphinine has so far been prepared in solution and spectroscopically~ haracterized.'~] There is also very little known about phosphorus-rich benzene analogues. A cyclotrimerization product of terf-butylphosphaethyne lf41 has been characterized as a x-bound triphosphadewarben~ ene.[~] A second trimerization product of 1 was postulated to be a coordinated 1, 3, 5-tripho~ phinine;[~' this, however, has not yet been definitively proven.['] We report here an efficient synthesis of 1 L3, 3L3-diphosphinines in the coordination sphere of iron (o) by [2+ 2+ 21 cycloaddition of two phosphadkynes and a terminal alkyne. The release of these ll3, 3A3-diphosphinines under oxidative conditions is also discussed.