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

使用改性杂多阴离子载体合成和分子设计杂多阴离子负载的有机金属化合物

基本信息

批准号：
03640529
负责人：
NOMIYA Kenji
金额：
$ 1.22万
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：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

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.

根据1992年的资助申请，已经进行了（1）改性的杂多阴离子载体的制备和（2）有机金属阳离子物种和杂多阴离子负载的有机金属化合物的制备。本研究取得的一些新成果如下：1.对于Dawson型杂多阴离子[<15>P_2W_Nb_3O_<62>]_<9->（2-x），（Bu_4N）_9盐是乙腈可溶的非晶态，意外地以~ 20 mg级收率得到了晶态Na_9盐，其结构已由单晶X射线衍射分析确定。在本研究中，成功地分离出了一种水溶性的结晶形式Na_9[P_2W_Nb_3O_ ]·23H_2O，合成规模为13 g，产率为61%<15><62>。该化合物可作为有机金属阳离子物种的新载体，发展为杂多阴离子负载有机金属化合物晶型的合成，也可作为均相氧化催化剂。对于Keggin型杂多阴离子[SiW_9Nb_3O_<40>]_<7->（1-x），首次合成了一种水溶性结晶Na_7盐（3g，产率62%），其结构为Na_7[SiW_9Nb_3O_<40>]·16H_2O。该Na_7盐可用于合成结晶型杂多阴离子负载的有机金属化合物，也可用作均相氧化催化剂。以<15><62>Dawson型改性的杂多化合物（Bu_4N）_9[<15>P_2W_Nb_3O_<62>]和单独制备的有机金属配合物[Cp^*RhCl_2]_2为原料，合成了新型杂多阴离子负载的有机金属化合物（Bu_4N）_4Na_3[Cp^*Rh·P_2W_Nb_3O_ ]（Cp^* = C_5Me_5）。虽然该化合物还不是晶体，但用上述Na_9[P_2W_Nb_3O_ ]·23H_2O盐有望分离出[Cp^*Rh·<15>P_2W_Nb_3O_<62>]^<7-><15><62>的晶体形式。