FERROCENYL-SUBSTITUTED PHOSPHENIUM CATIONS AND PHOSPHIDE ANIONS
FERROCENYL-SUBSTITUTED PHOSPHENIUM CATIONS AND PHOSPHIDE ANIONS
复制标题
DOI：
10.1021/ic00165a022
复制
发表时间：
1983-01-01
影响因子：
4.6
通讯作者：
SENA, SF
中科院分区：
文献类型：
--
作者：
BAXTER, SG;COLLINS, RL;SENA, SF
（五）、用化学计量的Al 2Cl 6的二氯甲烷溶液处理Fc2 PCl（4）、6或5，分别得到磷离子的四氯铝酸盐[Fc 2 P]+（7）、[Fc（Me 2N）P] 4（8）或[Fc（Cl）P]+（9）。报道了所有三种盐的~（31）P、~（27）Al和~ 1H NMR数据，并通过~（57）Fe穆斯堡尔谱证实了7作为二茂铁基化合物的结构。当用过量的A12 C16处理5时，没有发现[FcP] 2+形成的证据。7的刘易斯酸性通过与m-Bu 3 P反应来证明，其产生加合物[n-Bu 3 PPFc 2] 4 [A] C14]-（10）。在正己烷中，4与Fe_2（CO）_9反应，合成了铁羰基配合物（Fe_2Cl）Fe（CO）_4（11）。用化学计量的Al_2Cl_（1-）在CH_2Cl_2溶液中处理11，得到配位的膦离子配合物[Fe_2 PFe（CO）_4]+[AlCl_4]_（12）。12的57 Fe穆斯堡尔谱数据表明，磷离子占据了铁三角双锥的轴向位置。在Et 2 O中用LiAlH 4还原4得到仲膦Fc2 PH（13），其可以用n-BuLi锂化成Fc2 PLi（14）。用D2 G处理14个产生Fc 2 PD（15）。二膦Fc2 PPFc 2（16）可以通过4与K、Mg或萘钠在THF中的反应来制备。
(5). Treatment of Fc^ PCl (4), 6, or 5 with a stoichiometric quantityof Al2Cl6 in CH2Cl2 solution results in tetrachloroaluminate salts of the phosphenium ions [Fc2P]+(7),[Fc (Me2N) P] 4 (8), or [Fc (Cl) P]+(9), respectively. 31P, 27Al, and* H NMR data are reported for all three salts, and the formulationof 7 as a ferrocenyl compound was confirmed by 57Fe Mossbauer spectroscopy. No evidence for [FcP] 2+ formation was found when 5 was treated with excess A12C16. The Lewis acidity of 7 was demonstrated by reaction with m-Bu3P, which results in the adduct [«-Bu3PPFc2] 4 [A] C14]“(10). The iron carbonyl complex (Fc2PCl) Fe (CO) 4 (11) was prepared by the reactionof 4 with Fe2 (CO) 9 in «-hexane. Treatmentof 11 with a stoichiometric quantity of A12C1< in CH2C12 solution affords the coordinated phosphenium ion complex [Fc2PFe (CO) 4]+[AlCl4]"(12). 57Fe Mossbauer data for 12 suggest that the phosphenium ion occupies an axial site of the irontrigonal bipyramid. Reduction of 4 with LiAlH4 in Et20 affords the secondary phosphine Fc2PH (13), which can be lithiated to Fc2PLi (14) with n-BuLi. Treatment of 14 with D2G produced Fc2PD (15). The diphosphine Fc2PPFc2 (16) can be prepared via the reaction of 4 with K, Mg, or sodium naphthalenide in THF.