Paddlewheel-type dirhodium complexes with N,N’-bridging ligands
Paddlewheel-type dirhodium complexes with N,N’-bridging ligands
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DOI：
10.1016/j.ccr.2022.214997
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发表时间：
2023-03
影响因子：
20.6
通讯作者：
Y. Kataoka;Natsumi Yano;M. Mikuriya;M. Handa
中科院分区：
文献类型：
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作者：
Y. Kataoka;Natsumi Yano;M. Mikuriya;M. Handa
叶轮型二铑（Rh2）与N,N'-桥配体（如甲酰胺离子）的配合物，其双核核心内具有单键，具有氧化还原活性，并根据Rh2键赤道和轴向位置的配位配体种类而采用四种氧化态（Rh23+、Rh24+、Rh25+和Rh26+）。N,N'-桥配体具有很强的氧化还原性。 σ-供体能力，显着引起π*(Rh2)和δ*(Rh2)轨道的不稳定，与其他O,O'-和N,O-桥配体相比，与金属中心强烈配位。因此，具有N,N’桥配体的Rh2配合物表现出独特的近红外吸收和电化学性能。本综述总结了带有N,N'-桥配体的叶轮型Rh2配合物[Rh2(L)4]（L =N,N'-二芳基甲脒、2-苯胺基吡啶等）的合成、晶体结构、电化学行为、吸收特征和磁性。
Paddlewheel-type dirhodium (Rh2) complexes withN,N’-bridging ligands such as formamidate ions, which have a single bond within the dinuclear core, are redox-active and adopt four oxidation states (Rh23+, Rh24+, Rh25+, and Rh26+) depending on the kinds of coordination ligands at the equatorial and axial positions of the Rh2bond.N,N’-bridging ligands possess a strong σ-donating ability, which significantly induces the destabilization of π*(Rh2) and δ*(Rh2) orbitals, and strongly coordinate to the metal center compared with otherO,O’- andN,O-bridging ligands. Therefore, Rh2complexes withN,N’-bridging ligands show unique near-infrared absorption and electrochemical properties. This review summarizes the synthesis, crystal structures, electrochemical behaviors, absorption features, and magnetic properties of paddlewheel-type Rh2complexes withN,N’-bridging ligands, [Rh2(L)4] (L =N,N’-diarylformamidinate, 2-anilinopyridinate, etc.).