Synthesis and Molecular Design of Water-Soluble, All-Sodium Salts of Heteropolyanion-Supported Organometallic Complexes

根据1995年补助金的应用， （1）对改良道森-和凯根-型异丁二烯盐的制备;（2）对有机金属化国家物种Cp^<*>Rh^<2+> （Cp^<**>=C_5Me_5）的制备;（3）对水溶剂的制备;异丁二烯支持的有机化合物的制备。从这项研究中获得了一些新的结果：1.使用Dawson型修改异丁二烯钠Na_9 [<15>P_2W_Nb_3O_<62>] ·23H_2O作为支持，目标化合物的合成条件Na_7 [Cp^&lt;*&gt;Rh·<15>P_2W_Nb_3O_<62>]已测试。此混合物由硝基下混合DMSO/CH_3CN （10毫升/50毫升）填充4小时。旁路导管NaBF_4被DMSO/EtOAc重复重复复制。The purified compound with a formula of Na_7 [Cp^\*&gt;Rh·P_2 W_<15>Nb_3 O_<62>] ·7 DMSO·5 H_2 O was characterized by full elemental analyzes， TG/DTA，FT-IR，GLC analysis and NMR （^<183>W，^<31>P，^1 H，^<13>C）spectroscopy. 2.这一综合征是以Bu_4N盐为基础的传统化合物有明显不同的区别。根据类似的方法，支持Keggin型Na_7 [SiW_9Nb_3O_]的复合<40>体·16H_2O支持已被运送。目标复合物由84 ℃下硝酸盐混合DMSO/CH_3CN （7.2 mL/34 mL）溶液形成。The crude compound obtained here still contained some positional isomers of the supported Cp^\*&gt;Rh^&lt;2+&gt; group。单个异构体在3小时84 ℃ C下再次加热，以干燥DMSO下的硝酸盐为基础，以净化为基础，与DMSO/EtOAc重复的重复。目标复合物的组成由Na_5 [Cp^&lt;**&gt;Rh·SiW_9Nb_3O_<40>] ·3DMSO·2H_2O表征为全元素分析、TG/DTA、FT-IR和NMR （^<183>W，^<31>P，^1H，^<13>C）光谱分析。

According to the Application for the Grant in 1995, (1) preparation of all-soidum salts of modified Dawson- and Keggin-type heteropolyanion-supports and (2) preparation of organometallic cation-species Cp^<**>Rh^<2+> (Cp^<**>=C_5Me_5) and (3) preparations of the water-soluble, all-sodium salts of heteropolyanion-supported organometallic complexes have been performed. Something new results obtained from this research are as follows :1. Using the sodium salt of Dawson-type modified heteropolyanion Na_9 [P_2W_<15>Nb_3O_<62>] ・23H_2O as a support, the synthetic conditions of the target compound Na_7 [Cp^<**>Rh・P_2W_<15>Nb_3O_<62>] were examined. This compound was formed by refulxing for 4 hr in mixed DMSO/CH_3CN (10 mL/50 mL) under nitrogen. Byproduct NaBF_4 was removed by repeated reprecipitations with DMSO/EtOAc. The purified compound with a formula of Na_7 [Cp^<**>Rh・P_2W_<15>Nb_3O_<62>] ・7DMSO・5H_2O was characterized by full elemental analyzes, TG/DTA,FT-IR,GLC analysis and NMR (^<183>W,^<31>P,^1H,^<13>C) spectroscopy.2. This synthesis was quite different from those of the traditional compound based on the Bu_4N salts.3. By similar method, the preparation of the corresopnding Cp^<**>Rh^<2+> complex supported on Keggin-type Na_7 [SiW_9Nb_3O_<40>] ・16H_2O support was carried out. The target compound was formed by the 4 hr-reaction at 84ﾟC under nitrogen in mixed DMSO/CH_3CN (7.2 mL/34 mL) solvent. The crude compound obtained here still contained some positional isomers of the supported Cp^<**>Rh^<2+> group. The single isomer was obtained by heating again for 3 hr 84ﾟC in dry DMSO under nitrogen, followed by purification based on repeated reprecipitations with DMSO/EtOAc. The composition of the target compound was determined as Na_5 [Cp^<**>Rh・SiW_9Nb_3O_<40>] ・3DMSO・2H_2O by characterization with full elemental analysis, TG/DTA,FT-IR and NMR (^<183>W,^<31>P,^1H,^<13>C) spectroscopy.