Synthesis and Molecular Design of Heteropolyanion-Supported Organometallics Using Modified Heteropolyanion-Support

点击翻译按钮获取中文摘要

According to the Application for the Grant in 1992, (1) the preparation of modified heteropolyanion-supports and (2) the preparations of organometallic cation-species and the heteropolyanion-supported organometallic compounds have been performed. Something new results obtained from this research are as follows :1. For Dawson-type modified heteropolyanion [P_2W_<15>Nb_3O_<62>]^<9->, the previously reported (Bu_4N)_9 salt was acetonitrile-soluble and non-crystalline, and the crystalline Na_9 salt was obtained unexpectedly with - 20 mg order yield, the structure of which has been determined by a single- crystal X-ray diffraction analysis. In this research, a water-soluble and crystalline from of the Na_9 salt has been successfully isolated with synthetic scale (13 g, 61 % yield) as Na_9[P_2W_<15>Nb_3O_<62>]・23H_2O. This compound can be used as a new support for organometallic cation-species which will develop into the synthesis of a crystalline form of the heteropolyanion-supported organometallic compound, and can be also utilized as a homogeneous oxidation-catalyst.2. For Keggin-type modified heteropolyanion [SiW_9Nb_3O_<40>]^<7->, a water-soluble crystalline Na_7 salt has been first isolated with synthetic scale (3 g, 62 % yield) as Na_7[SiW_9Nb_3O_<40>]・16H_2O. This Na_7 salt can develop into the syntheses of crystalline heteropolyanion-supported organometallics and itself can also be utilized as a homegeneous oxidation-catalyst.3. New heteropolyanion-supported organometallic compound (Bu_4N)_4Na_3[Cp^*Rh・P_2W_<15>Nb_3O_<62>] (Cp^* = C_5Me_5) has been synthesized using a Dawson-type modified hetero-poly compound (Bu_4N)_9[P_2W_<15>Nb_3O_<62>] and a separately prepared organometallic complex [Cp^*RhCl_2]_2. Although this compound is not crystalline yet, an isolation of the crystalline form of [Cp^*Rh・P_2W_<15>Nb_3O_<62>]^<7-> will be promised using the above Na_9[P_2W_<15>Nb_3O_<62>]・23H_2O salt.