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^<**>Rh^<2+> (Cp^<**>= c_5 me_5) and (3)preparations of the water-soluble，all-sodium salts of heteropolyanion-supported organometallic complexes已表现。以下是研究成果：1.使用sodium salt ofDawson-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 4hr in mixed DMSO/ ch_3cn (10ml / 50ml) under nitrogen.Byproduct nabf_4 was removed by repeated reprecipitations with DMSO/EtOAc. The purified compoundwith a formula of na_7 [Cp^<**>Rh·p_2w_< 15> nb_3o_< 62>] 7dmso·5h_2was characterized by fullelemental analyzes,TG/DTA,FT-IR,GLC analysis and NMR (^<183>W,^<31>P,^ 1h,^<13>C) spectroscopy.2. This synthesis wasquite different from those of the traditional compound based on the bu_4n salts.3. By similarmethod,the preparation of the corresopnding Cp^<**>Rh^<2+> complex supported on Keggin-type na_7[siw_9 nb_3o_ <40>] 16h_2 O support was carried out. The target compound was formed by The 4hr-reaction at 84゚C under nitrogen in mixed DMSO/ ch_3cn (7.2 mL/34 mL) solvent. The crude compoundobtained here still contained some positional isomers of the supported Cp^<**>Rh^<2+> group. thesingle isomer was obtained by heating again for 3hr 84゚C in dry DMSO under nitrogenfollowed by purification based on repeated reprecipitations with DMSO/EtOAc. The composition of Thetarget compound was determined asna_5 [Cp^<**>Rh·siw_9 nb_3o_ <40>] 3dmso·2h_2o by characterizationwith full elemental analysis, TG/DTA,FT-IR and NMR (^<183>W,^<31>P,^ 1h,^<13>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.