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

杂多阴离子负载有机金属配合物的水溶性全钠盐的合成和分子设计

• 批准号: 06640735
• 负责人: NOMIYA Kenji
• 金额: $ 1.34万
• 依托单位: Kanagawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06640735/
• 关键词: Heteropolytungstate; Modified heteropolyanion; Heteropolyanion-support; Trisubstituted Dawson-structure; Trisubstituted Keggin-structure; Organometallic cation species; All-soidum salt; Synthesis

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.

根据1995年的资助申请，（1）制备了改性Dawson和Keggin型杂多阴离子载体的全钠盐和（2）制备了金属有机阳离子物种Cp^** Rh^2+（Cp^**=C_5Me_5）和（3）制备了杂多阴离子负载的金属有机配合物的水溶性全钠盐。本研究取得的一些新成果如下：1.以Dawson型改性杂多阴离子Na 9 [P2 <15>WNb 3 O<62>] ·23 H2O为载体，研究了目标化合物Na 7 [Cp^** Rh·P2 <15>WNb 3 O]<62>的合成条件。该化合物通过在混合的DMSO/CH_3CN（10 mL/50 mL）中在氮气下回流4小时形成。通过用DMSO/EtOAc重复再沉淀除去副产物NaBF_4。通过<15><62>全元素分析、TG/DTA、FT-IR、GLC分析和NMR（~ 1 W，<183>~ 1 <31>P，~ 1H，~ 1C<13>）等手段对产物进行了表征，其分子式为Na_7 [Cp^**&gt;Rh·P_2W_ Nb_3O_ ] ·7 DMSO·5H_2O.该合成方法与传统的Bu_4N盐化合物的合成方法有很大的不同.用类似的方法，制备了以Keggin型Na_7 [SiW_9Nb_3O_ ] ·16H_2O为载体的Cp^~（**）Rh^~（2+）配合<40>物。目标化合物通过在84 ° C下在氮气下在混合的DMSO/CH_3CN（7.2mL/34 mL）溶剂中反应4小时形成。这里得到的粗化合物仍然含有负载的Cp^** Rh^2+基团的一些位置异构体。通过在氮气下在无水DMSO中在84 ° C下再次加热3小时，然后基于用DMSO/EtOAc重复再沉淀进行纯化，获得单一异构体。通过<40>全元素分析、TG/DTA、FT-IR和NMR（~ 1 <183>W，~ 1 <31>P，~ 1H，~ 1C<13>）等手段对产物进行了表征，确定了目标化合物的组成为Na_5 [Cp^**&gt;Rh·SiW_9Nb_3O_ ] ·3DMSO·2H_2O。

项目成果

K. Nomiya et al.: "The all-sodium salt of a golyoxoanion-sirpported organometallic complex" J. Organometal. Chem.505. 23-28 (1995)

K. Nomiya 等人：“Golyoxoanion-sirpported 有机金属络合物的全钠盐”J. Organometal。

K.Nomiya et.al.: "The all-sodium salt of a polyoxoanion-supported organometallic complex Na_7 [Cp^<**>Rh・P_2W_<15>Mb_3O_<62>] ・7DMSO・5H_2O" J.Organometal.Chem.Vol.505. 23-28 (1995)

K.Nomiya 等人：“多氧阴离子负载的有机金属配合物 Na_7 的全钠盐 [Cp^<**>Rh・P_2W_<15>Mb_3O_<62>] ・7DMSO・5H_2O” J.Organometal.Chem .第505卷23-28（1995）

K.Nomiya,et al.: "The all-sodium salt of a polyoxoanion-supported organometallic complex,Na_7[Cp^*Rh・P_2W_<15>Nb_3O_<62>]・7DMSO・5H_2O" J.Organometal.Chem.505. 23-28 (1995)

K.Nomiya等人：“多氧阴离子负载的有机金属络合物的全钠盐，Na_7[Cp^*Rh・P_2W_<15>Nb_3O_<62>]・7DMSO・5H_2O” J.Organometal.Chem.505 .23-28 (1995)