反芳香族B,N-カルベンσ配位子の開発と常磁性/アニオン性金錯体の合成と物性解明

反芳香族 B,N-卡宾 σ 配体的开发、顺磁/阴离子金配合物的合成以及物理性质的阐明

• 批准号: 21K05099
• 负责人: SHANG RONG
• 金额: $ 2.75万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2021
• 资助国家: 日本
• 起止时间: 2021-04-01 至 2024-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-21K05099/
• 关键词: main group ligand; electronic tuning; redox active ligand; Aurate; Carbene; boron; 反芳香族σ配位子; 有機遷移金属化学; 機能性材料

The interplay of aromaticity and antiaromaticity of conjugated π systems is a crucial design strategy for tuning light-initiated electron-transfer properties in designing functional molecules. For transition metal (TM) photocatalysts, while heterocyclic aromatic ligands are widely used for modulation of their (photo)redox behaviors, the effect of antiaromatic ligands remains poorly understood due to a lack of synthetic methodologies. This project proposed a design and synthesis to isolate radical and anionic gold complexes bearing a 4π B, N-heterocyclic Carbene (BNC). The expected antiaromaticity and the inclusion of boron atoms in BNC results in its super π-accepting and σ-donating abilities which are ideal to stabilize and tune unusual oxidation states and radical behaviors of the metal.The synthesis of several derivatives of BNC Au(I) complexes were established. A 2e reduction of the (BNC-Cl)AuL complex by lithium allowed isolation of a bright orange lithium aurate complex Li[(BNC)AuL]. Computational analysis indicated that, despite of the 4π electron counting, the neutral BNC ligand on Au(I) is mostly non-aromatic in character, due to the localized BN π bonds. After reduction, the gold center remained as +I, whereas the BNC moiety became a 6π aromatic system. In particular, the occupied p orbital at the ligating carbon center was shown to interact strongly with the Au(I) 6p orbital with an interaction energy between 15.5 kcal/mol. This result showed that the gold(I) can form multiple bonds with ligand through its 6p orbital ligands instead of 5d orbitals.

共轭π系统的芳香性和抗洞穴性相互作用是在设计功能分子中调整光引发电子转移特性的关键设计策略。对于过渡金属（TM）光催化剂，虽然杂环芳香族配体被广泛用于调节其（照片）氧化还原行为，但由于缺乏合成方法，抗洞察配体的效果仍然很糟糕。该项目提出了一种设计和合成，以隔离带有4πb，n-杂环碳纤维（BNC）的自由基和阴离子金络合物。 BNC中的预期抗鉴别性和硼原子的包含导致其超级π受感应和σ降低能力，非常适合稳定和调整金属的异常氧化物和自由基行为。通过锂减少（BNC-CL）AUL复合物的2E允许分离明亮的橙色锂锂复合物LI [（BNC）AUL]。计算分析表明，由于局部BNπ键，Au（i）上的4π电子计数的目的地中，Au（i）上的中性BNC配体在特征上主要是非芳香的。还原后，金中心保持为 +I，而BNC部分成为6π芳族系统。特别地，显示在连接碳中心的占用的P轨道与AU（I）6p轨道相互作用，与15.5 kcal/mol之间的相互作用能相互作用。该结果表明，黄金（i）可以通过其6p轨道配体而不是5D轨道形成多种键。

项目成果

Gas‐Phase Characterization of Hypervalent Carbon Compounds Bearing 7‐6‐7‐Ring Skeleton: Penta‐/Tetra‐Coordinate Isomers

带有 7-6-7 环骨架的高价碳化合物的气相表征：五配位/四配位异构体

• DOI: 10.1002/chem.202203163
• 发表时间: 2023
• 期刊: Chemistry - A European Journal
• 作者: Muramatsu Satoru;Ohshimo Keijiro;Shi Yuan;Kida Motoki;Shang Rong;Yamamoto Yohsuke;Misaizu Fuminori;Inokuchi Yoshiya
• 通讯作者: Inokuchi Yoshiya

Dipyrido-Annulated N-Heterocyclic Carbene-Based Pincer Ligands And Their Complexation To Late Transition Metals

双吡啶环N-杂环卡宾钳配体及其与后过渡金属的络合

• 发表时间: 2021
• 作者: Rong Shang;Kazuki Nakanishi;Sihan Zhang;Naoto Maeta;and Yohsuke Yamamoto;Seiji Yamazoe
• 通讯作者: Seiji Yamazoe

A boron, nitrogen-containing heterocyclic carbene (BNC) as a redox active ligand: synthesis and characterization of a lithium BNC-aurate complex

作为氧化还原活性配体的含硼氮杂环卡宾（BNC）：BNC-金酸锂配合物的合成和表征

• DOI: 10.1039/d2dt01083f
• 发表时间: 2022
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Kimura Yoshitaka;Lugo-Fuentes Leonardo I.;Saito Souta;Jimenez-Halla J. Oscar C.;Barroso-Flores Joaquin;Yamamoto Yohsuke;Nakamoto Masaaki;Shang Rong
• 通讯作者: Shang Rong

University of Guanajuato/National Autonomous University of Mexico(メキシコ)

瓜纳华托大学/墨西哥国立自治大学（墨西哥）

Developments of main-group ligands for transition metal complexes: a journey of unexpected reactivity

过渡金属配合物主族配体的发展：意想不到的反应之旅

• 发表时间: 2022
• 作者: Rong Shang*;Yoshitaka Kimura;Leonardo I. Lugo-Fuentes;Souta Saitou;Shu Furukawa;J. Oscar C. Jiminez-Halla;Joaquin Barroso-Flores;Masaaki Nakamoto;Yohsuke Yamamoto;Hiroto Yoshida
• 通讯作者: Hiroto Yoshida