Synthesis and characterisation of ferrocenyl-phosphonic and -arsonic acids
Synthesis and characterisation of ferrocenyl-phosphonic and -arsonic acids
复制标题
DOI：
10.1016/s0022-328x(01)00908-1
复制
发表时间：
2001-12-03
影响因子：
2.3
通讯作者：
Henderson, W
中科院分区：
文献类型：
--
作者：
Alley, SR;Henderson, W
二茂铁衍生酸FcCH（2）CH（2）E（O）（OH）（2）[4，E = P; 10，E = As; Fc = Fe（eta（5）-C5 H5）（eta（5）-C5 H4）]是通过FcCH（2）CH（2）Br与P（OEt）（3）反应后水解或与亚砷酸钠反应后酸化而合成的。FcCH（2）OH与（Eto）（2）P（O）Na反应得到FcP（O）（OEt）（OH），其通过使用Me 3SiBr-Et 3 N的甲硅烷基酯水解、随后通过水处理而转化为FcCH（2）P（O）（OH）（2）（3）。类似地，已知的膦酸FcP（O）（OH）2和新的衍生物1，1 '-Fc'[P（O）（OH）（2）]（2）[Fc '= Fe（eta（5）-C5 H4）（2）]和1，1'-Fc '[CH_2 P（O）（OH）（2）]（2）（7）已经通过它们相应的酯合成。对3和7进行了X射线晶体结构测定，并讨论了氢键网络。电喷雾质谱法已被用于各种酸的表征。膦酸给出预期的[M-H]（-）离子，并且已经发现它们在升高的锥电压下的碎裂取决于酸。FcP（O）（OH）（2）断裂成[C5 H4 PO 2 H]（-），而Fc（CH 2）（n）P（O）（OH）（2）（n = 1，2）则生成Fe{eta（5）-C5 H4（CH 2）（n）P（O）O-2]（-）离子，推测Fe原子与膦酸酯基团之间存在分子内相互作用。与此相反，胂酸（10）。与PhAs（O）（OH）（2）一起进行比较，经历容易的烷基化（在甲醇或乙醇溶剂中），并在升高的锥电压（例如> 60 V）下经历碳-砷键断裂，得到[CpFeAs（O）（OR）O]（-）（R = H，Me，Et）并最终得到[AsO 2]（-）离子。(C)2001爱思唯尔科技有限公司。保留所有权利。
The ferrocene-derived acids FcCH(2)CH(2)E(O)(OH)(2) [4, E = P; 10, E = As; Fc = Fe(eta (5)-C5H5)(eta (5)-C5H4)] have been synthesized by the reaction of FcCH(2)CH(2)Br with either P(OEt)(3) followed by hydrolysis, or with sodium arsenite followed by acidification. Reaction of FcCH(2)OH with (Eto)(2)P(O)Na gave FcP(O)(OEt)(OH), which was converted to FcCH(2)P(O)(OH)(2) (3) by silyl ester hydrolysis using Me3SiBr-Et3N followed by aqueous work-up. Similarly, the known phosphonic acid FcP(O)(OH)2 and the new derivatives 1,1'-Fc'[P(O)(OH)(2)](2) [Fc'= Fe(eta (5)-C5H4)(2)] and 1,1'-Fc'[CH2P(O)(OH)(2)](2) (7) have been synthesized via their corresponding esters. X-ray crystal structure determinations have been carried out on 3 and 7, and the hydrogen-bonding networks discussed. Electrospray mass spectrometry has been employed in the characterization of the various acids. Phosphonic acids give the expected [M-H](-) ions and their fragmentation at elevated cone voltages has been found to be dependent on the acid. FcP(O)(OH)(2) fragments to [C5H4PO2H](-), but in contrast Fc(CH2)(n)P(O)(OH)(2) (n = 1, 2) give Fe{eta (5)-C5H4(CH2)(n)P(O)O-2](-) ions, which are proposed to have an intramolecular interaction between the Fe atom and the phosphonate group. In contrast, arsonic acid (10). together with PhAs(O)(OH)(2) for comparison, undergo facile alkylation (in methanol or ethanol solvent), and at elevated cone voltages (e.g. > 60 V) undergo carbon-arsenic bond cleavage giving [CpFeAs(O)(OR)O](-) (R = H, Me, Et) and ultimately [AsO2](-) ions. (C) 2001 Elsevier Science B.V. All rights reserved.