Transition Metal Complexes with Multiple Ligand Bonds as the Lewis Base Component of Frustrated Lewis Pairs

具有多个配体键的过渡金属配合物作为受阻路易斯对的路易斯碱组分

• 批准号: 1664973
• 负责人: Elon Ison
• 金额: $ 44.99万
• 依托单位: North Carolina State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-05-01 至 2021-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664973&HistoricalAwards=false
• 关键词: Transition; Metal; Complexes; Multiple; Ligand

The design and discovery of new catalysts, and new catalytic transformations, is critical for the efficient utilization of our natural resources. With this award from the Chemical Catalysis Program of the NSF Division of Chemistry, Professor Ison is developing catalysts that contain a bond between an oxygen atom and a transition metal, specifically rhenium. The rhenium-oxygen bond has unique reactivity that is being used to develop fundamentally new catalytic reactions. For example, new ways to convert carbon dioxide into useful chemicals are being investigated. Dr. Ison is involved in a variety of outreach efforts aimed at recruiting high school and undergraduate students to pursue careers in STEM fields. In addition, Dr. Ison is engaged in the training of high school teachers to incorporate aspects of his research into the high school science curriculum.This award from the Chemical Catalysis Program of the Chemistry Division supports research by Dr. Elon Ison who is designing new catalysts that contain a rhenium-ligand multiple bond. In this approach, five-coordinate square pyramidal complexes with a terminal multiple bond to a heteroatom in the apical position are utilized so that the electronic consequences of this geometric arrangement can be used to develop catalysts for the activation of small molecules. Dr. Ison is developing a new type of frustrated Lewis pair (FLP) catalyst, where a transition metal oxo acts as the Lewis base component. These new FLPs are effective as catalysts for hydrogenation, and involve a new mechanism for substrate activation by a transition metal complex where the metal does not directly participate, but instead plays an ancillary role. Fundamental mechanistic studies as well as high-level density functional theory(DFT) calculations are being used to understand the structure and reactivity of these FLPs and to design new catalytic systems In this project, Dr. Ison is developing FLP catalyst for asymmetric hydrogenations and the activation of carbon dioxide. Dr. Ison is involved in a variety of outreach efforts aimed at recruiting high school and undergraduate students to pursue careers in STEM fields. In addition, Dr. Ison is engaged in the training of high school teachers to incorporate aspects of his research into the high school science curriculum.

设计和发现新的催化剂，以及新的催化转化，对于有效利用我们的自然资源至关重要。凭借美国国家科学基金会化学部化学催化项目的奖项，艾森教授正在开发一种包含氧原子和过渡金属（特别是铼）之间键的催化剂。铼-氧键具有独特的反应活性，正被用于开发全新的催化反应。例如，正在研究将二氧化碳转化为有用化学物质的新方法。Ison博士参与了各种旨在招募高中和本科生从事STEM领域职业的外展工作。此外，Ison博士还从事高中教师的培训，将他的研究纳入高中科学课程。该奖项来自化学部门的化学催化项目，支持伊隆·伊森博士的研究，他正在设计含有铼配体多重键的新型催化剂。在这种方法中，利用五坐标方形锥体配合物，在顶端位置有一个末端多键到杂原子，因此这种几何排列的电子后果可以用来开发小分子活化的催化剂。艾森博士正在开发一种新型的受挫刘易斯对（FLP）催化剂，其中过渡金属氧作为刘易斯碱组分。这些新的FLPs作为氢化催化剂是有效的，并且涉及一种新的机制，即由过渡金属配合物激活底物，其中金属不直接参与，而是起辅助作用。基础机理研究和高密度泛函理论（DFT）计算被用于了解这些FLP的结构和反应性，并设计新的催化系统。在这个项目中，Ison博士正在开发用于不对称氢化和二氧化碳活化的FLP催化剂。Ison博士参与了各种旨在招募高中和本科生从事STEM领域职业的外展工作。此外，Ison博士还从事高中教师的培训，将他的研究纳入高中科学课程。

项目成果

Synthesis and Reactivity of Re(III) and Re(V) Fischer Carbenes

Re(III) 和 Re(V) 费歇尔卡宾的合成和反应性

• DOI: 10.1021/acs.organomet.9b00600
• 发表时间: 2020
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Brown, Caleb A.;Lilly, Cassandra P.;Lambic, Nikola S.;Sommer, Roger D.;Ison, Elon A.
• 通讯作者: Ison, Elon A.

Energy Decomposition Analysis of Lewis Acid/Base Adducts and Frustrated Lewis Pairs: The Use of E Orb / E Steric Ratios as a Reaction Parameter

路易斯酸/碱加合物和受抑路易斯对的能量分解分析：使用 E Orb / E 空间比作为反应参数

• DOI: 10.1021/acs.inorgchem.1c00911
• 发表时间: 2021
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Ison, Elon A.;Tubb, Joshua L.
• 通讯作者: Tubb, Joshua L.