Development ofa new class of complexes of pyrazolates

新型吡唑酸盐配合物的开发

• 批准号: 15550053
• 负责人: UMAKOSHI Keisuke
• 金额: $ 2.43万
• 依托单位: Nagasaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550053/
• 关键词: palladium; platinum; gold; silver; cyclic trinuclear cimplex; pyrazole; mixed-valence complex; isomerization; 混合金属錯体; 多核錯体; X線構造解析

Polynuclear transition metal complexes with pyrazoles and/or pyrazolates have been attracting much attention because of their versatile structures and properties. By using the bridging ability of pyrazolates, it is possible to construct cyclic polynuclear complexes. Although tetranuclear, hexanuclear, or octanuclear cyclic complexes are also known, the most popular cyclic complex is the trinuclear one, in which monovalent two-coordinate metal ions are singly bridged by pyrazolates to form [M^I_3(μ-Rpz)_3](M=Ag,An,Cu,Co;Rpz=pyrazolate or substituted pyrazolates). We have been thinking the possibility that pyrazolates can form cyclic trinuclear complexes with various transition metals such as acetates, and thus we have conducted this project.In this project, we have succeeded to synthesize the cyclic trinuclear palladium(II) complex [Pd3(μ-pz)_6], which has very similar structure to [Pd_3(μ-pz)_6]. It prompted us to make metal-metal bonding by using [Pt_3(μ-pz)_3], because [Pd_3(μ-pz)_6] is hard to oxidize due to smaller distribution of 4d orbital. Actually, we have succeeded to oxidize [Pt_3(μ-pz)_6]. The partially oxidized Pt(II,III,III)_3 species [Pt_3Br_2(μ-pz)_6] has intense blue color, which was attributed to the dσ→dσ^* transition (HOMO-LUMO transition).

吡唑类和/或吡唑酸酯类的多核过渡金属配合物因其结构和性质的多样性而受到广泛的关注。利用吡唑酸酯的桥接能力，可以构建环状多核配合物。虽然也有四核、六核或八核环配合物，但最常见的环配合物是三核环配合物，其中一价双配位金属离子被吡唑酸酯单桥接形成[M^I_3(μ-Rpz)_3]（M=Ag,An,Cu,Co;Rpz=吡唑酸酯或取代吡唑酸酯）。我们一直在思考吡唑酸盐与各种过渡金属（如醋酸盐）形成环状三核配合物的可能性，因此我们进行了这个项目。在本项目中，我们成功合成了环状三核钯（II）配合物[Pd3(μ-pz)_6]，其结构与[Pd_3(μ-pz)_6]非常相似。由于[Pd_3(μ-pz)_6]的四维轨道分布较小，不易氧化，这促使我们利用[Pt_3(μ-pz)_3]进行金属-金属成键。实际上，我们已经成功地氧化了[Pt_3(μ-pz)_6]。部分氧化的Pt(II，III，III)_3 [Pt_3Br_2(μ-pz)_6]呈现出强烈的蓝色，这是由dσ→dσ^*跃迁（HOMO-LUMO跃迁）引起的。

项目成果

Unusual Magetic Properties of the Edge-Sharing Bioctahedral Dirhenium(IV) Complex of Pyridine-2-thiolate

吡啶-2-硫醇盐共边双铼(IV)配合物的异常磁性能

• 发表时间: 2005
• 期刊: Angewandte Chemie International Edition 44(5)
• 作者: Prall;Parkinson;Fleming;Ishikawa;K.Umakoshi et al.
• 通讯作者: K.Umakoshi et al.

Pyrazolato-bridged polynuclear palladium and platinum complexes. Synthesis, structure, and reactivity.

• DOI: 10.1021/ic026196g
• 发表时间: 2003-05
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: K. Umakoshi;Y. Yamauchi;Keiko Nakamiya;T. Kojima;M. Yamasaki;H. Kawano;M. Ônishi