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年的赠款申请，（1）准备修改后的Dawson-和Keggin-Type Heteropolyanion-Supports以及（2）制备有机阳离子阳离子特性CP^<**> rh^<2+>（CP^<**> = C_5me_5）和（3）的（3）sod-sod-sod-sod-sod-sod-sod sodbul的准备，杂质支持的有机络合物已经进行了。从这项研究中获得的新结果如下：1。使用Dawson-Type的钠盐修饰的Hetolyanion Na_9 [P_2W_ <15> NB_3O_ <62>] ・23H_2O作为支持，目标复合Na_7 [CP^<**> RH p_2w_ P_2W_ P_2W_ p_2w_ p_2w_ p_2w_ p_2w_ <15> nb_3o_ <62o_ <62>]。该化合物是通过在氮中混合DMSO/CH_3CN（10 mL/50 mL）中启动4小时形成的。副产品NABF_4通过用DMSO/EtOAC重复重新沉淀去除。具有Na_7 [Cp^<**> RH的p_2w_ <15> NB_3O_ <62>]的纯化化合物，通过完整的元素分析，TG/DTA，FT-IR，FT-IR，GLC分析和NMR（^<183> W 31> p，^，^31> p，^1 H1 <31> p，<13> p p p_2w_ <**> NB_3O_ <62>] ・7DMSO ・7DMSO ・5H_2O。该合成与基于BU_4N沙拉的传统化合物的合成大不相同。3。通过类似的方法，在keggin-type na_7 [siW_9NB_3O_3O_ <40>] ・16H_2O支持上支持了Corsopnding cp^<**> rh^<2+>复合物。在混合DMSO/CH_3CN（7.2 mL/34 mL）溶剂中，在氮气下，在84°C下在84°C处的4 HR反应形成靶化合物。此处获得的粗化合物仍然包含受支持的CP^<**> rh^<2+>组的一些位置异构体。单个异构体是通过在氮气下在干燥DMSO中再次加热3小时84°C获得的，然后基于与DMSO/EtOAC反复重新沉淀的纯化。靶化合物的组成被确定为Na_5 [Cp^<**> Rh・SiW_9NB_3O_3O_ <40>] ・3DMSO ・2H_2O ・2H_2O通过表征进行完整元素分析，TG/DTA，FT-IR和NMR（^<183> w，^<183> w，^<183> w，^> p，^> p，^> p，^<31> p，^p，^1h，^1h，^<13> c）

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)