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

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^&lt；**&gt；Rh^&lt；2+&gt；(Cp^&lt；**&gt；=C_5Me_5)and(3)preparations of the water-soluble，all-sodium salts of heteropolyanion-supported organometallic compes have beperformed。Something new results obtained from this research are as follows：1.Using the sodium salt of Dawson-type modified heteropolyanion Na_9[P_2W_&lt；15&gt；Nb_3O_&lt；62&gt；]·23H_2O as a support，the synthetic conditions of the target compound Na_7[Cp^&lt；**&gt；Rh·P_2W_&lt；15&gt；Nb_3O_&lt；62&gt；]were examined.This compound was formed by refulxing for 4hr in mixed DMSO/CH_3CN(10mL/50mL)under nitrogen。Byproduct NaBF_4was removed by repeated reprecipitations with DMSO/EtOAc。The purified compound with a formula of Na_7[Cp^&lt；**&gt；Rh·P_2W_&lt；15&gt；Nb_3O_&lt；62&gt；]·7DMSO·5H_2O was characterized by full elemental analyzes，TG/DTA，FT-IR，GLC analysis and NMR(^&lt；183&gt；W，^&lt；31&gt；P，^1H，^&lt；13&gt；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^&lt；**&gt；Rh^&lt；2+&gt；complex supported on Keggin-type Na_7[SiW_9Nb_3O_&lt；40&gt；]·16H_2O support was carried out。The target compound was formed by the 4 hr-reaction at 84°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^&lt；**&gt；Rh^&lt；2+&gt；group。The single isomer was obtained by heating again for 3hr 84°C 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^&lt；**&gt；Rh·SiW_9Nb_3O_&lt；40&gt；]·3DMSO·2H_2O by characterization with full elemental analysis，TG/DTA，FT-IR and NMR(^&lt；183&gt；W，^&lt；31&gt；P，^1H，^&lt；13&gt；C)spectroscopy.

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.