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年的拨款申请，(1)制备了改性的Dawson和Keggin杂多阴离子载体的全固体盐；(2)制备了有机金属阳离子物种Cp^&lt；**&gt；2+&gt；(Cp^&lt；**&gt；=C_5Me_5)；(3)制备了水溶性全钠杂多阴离子负载的有机金属络合物。1.以Dawson型修饰杂多阴离子Na_9[P_2W_&lt；15&gt；Nb_3O_&lt；62&gt；]·23H_2O的钠盐为载体，考察了目标化合物Na_7[Cp^&lt；**&gt；Rh・P_2W_&lt；15&gt；Nb_3O_&lt；62&gt；]的合成条件。该化合物是在DMSO/CH3CN混合液(10毫升/50毫升)中于氮气中回流4小时形成的。副产物NaBF_4用DMSO/EtOAc反复再沉淀除去。通过全元素分析、TG/DTA、FT-IR、GLC分析和核磁共振波谱(^&lt；183&gt；W，^&lt；31&gt；P，^1H，^&lt；13&gt；C)对其结构进行了表征，得到了[Cp^&lt；**&gt；Rh・P_2W_&lt；15&gt；Nb_3O_&lt；62&gt；]·7DMSO·5H2O。这种合成方法与传统的以Bu_4N盐基化合物为基础的合成方法有很大不同。用类似的方法制备了Keggin-型Na_7[SiW_9Nb_3O_(40)&gt；]·16H_2O载体上相应的Cp^&lt；**&gt；Rh^&lt；2+&gt；目标化合物在84ﾟC氮气存在下，以二甲基亚砜/CH3CN(7.2m L/34 m L)混合溶剂为溶剂，反应4小时。这里得到的粗品仍含有一些支载的Cp^&lt；**&gt；Rh^&lt；2+&gt；基团的位置异构体。单异构体在干燥的二甲基亚砜中氮气中加热3小时84ﾟC，然后用二甲基亚砜/乙酸乙酯反复再沉淀纯化得到单一异构体。通过全元素分析、TG/DTA、FT-IR和核磁共振(^&lt；183&gt；W，^&lt；31&gt；P，^1H，^&lt；13&gt；C)光谱表征，确定目标化合物的组成为Na5[Cp^&lt；**&gt；Rh·SiW_9Nb_3O_&lt；40&gt；]·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)