Metal Complexes of the Carbon Dioxide Dianion

二氧化碳二价阴离子的金属配合物

• 批准号: 374707843
• 负责人: Professor Dr. Jun Okuda
• 金额: --
• 依托单位: Lehrstuhl für Metallorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/374707843?language=en
• 关键词: Metal; Complexes; Carbon; Dioxide; Dianion

The thermodynamically stable and kinetically inert substrate carbon dioxide can only be considered as a C1 source for synthesis and catalysis, if the effect of reducing agents on this molecule are fundamentally understood. This project deals with the synthesis, structural analysis and mechanistic studies of dinuclear complexes of carbon dioxide, which are derived from electropositive and oxophilic metals of groups 3 and 4. Combining ligands of varied electronic and steric properties with early transition metal centers of different electrophilicity/oxophilicity shall lead to new coordination modes. A particular focus is on the coordination of the nearly unexplored dianion CO22-, which is formally derived from doubly deprotonated dihydroxycarbene C(OH)2 and corresponds to the tautomer of formic acid. We assume that the chemical reduction of carbon dioxide within the coordination sphere of a metal may trigger further CO2 insertion and C-C bond forming reactions. After the new metal complexes with a chemically reduced form of CO2 will be synthesized, mechanistic studies will be performed. We expect new possibilities for metal mediated activation of carbon dioxide that goes beyond the hydrogenation to formic acid, methanol, or methane and shall lead to larger building blocks Cn>1 for synthesis.

只有从根本上了解了还原剂对二氧化碳分子的影响，热力学稳定、动力学惰性的底物二氧化碳才能被认为是合成和催化的碳源。本项目研究了由第3和第4族正电性和亲氧性金属衍生的二氧化碳双核配合物的合成、结构分析和机理研究。将具有不同电子和空间性质的配体与不同亲电性/亲氧性的早期过渡金属中心相结合将导致新的配位模式。一个特别的焦点是几乎未被探索的二阴离子CO22-的配位，它正式来自双去质子化的二羟基卡宾C(OH)2，对应于甲酸的互变异构体。我们认为，金属配位球内二氧化碳的化学还原可能会引发进一步的二氧化碳插入和C-C键形成反应。在合成了具有化学还原形式的二氧化碳的新的金属络合物之后，将进行机理研究。我们期待着金属介导的二氧化碳活化的新的可能性，它超越了氢化为甲酸、甲醇或甲烷，并将导致更大的构建块CN&GT；1用于合成。

项目成果

Reduced Arene Complexes of Scandium

• DOI: 10.1002/chem.202000946
• 发表时间: 2020-03
• 期刊: Chemistry (Weinheim an Der Bergstrasse, Germany)
• 作者: Priyabrata Ghana;A. Hoffmann;T. Spaniol;J. Okuda

Titanium(IV) Cations with Trigonal Monopyramidal Geometry: Unusual Lewis Acids Supported by a Triaryl Triamido-Amine Ligand.

具有三角单锥体几何形状的钛(IV)阳离子：三芳基三酰胺胺配体支持的不寻常的路易斯酸

• DOI: 10.1002/chem.201901796
• 发表时间: 2019
• 期刊: Chemistry
• 作者: van Krüchten;Spaniol
• 通讯作者: Spaniol

Formate complexes of titanium(IV) supported by a tris(phenolato)-amine ligand

三(酚基)-胺配体负载的钛(IV)甲酸盐配合物

• DOI: 10.1016/j.poly.2018.11.025
• 发表时间: 2019
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Höllerhage;van Krüchten;Spaniol
• 通讯作者: Spaniol

Carbonite, the dianion of carbon dioxide and its metal complexes

• DOI: 10.1016/j.jorganchem.2017.10.005
• 发表时间: 2017-10
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Albert Paparo;J. Okuda

Countercation Effect on CO2 Binding to Oxo Titanate with Bulky Anilide Ligands.

• DOI: 10.1002/chem.201803265
• 发表时间: 2018-10
• 期刊: Chemistry
• 作者: Albert Paparo;Jared S. Silvia;T. Spaniol;J. Okuda;C. Cummins