Sterically Encumbered Guanidinates for the Kinetic Stabilization and Study of Terminal Iron Nitrides in Weak Ligand Fields

空间位阻胍盐用于弱配体场中末端氮化铁的动力学稳定和研究

• 批准号: 1664938
• 负责人: Skye Fortier
• 金额: $ 38.31万
• 依托单位: University of Texas at El Paso
• 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: 2017-06-01 至 2022-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664938&HistoricalAwards=false
• 关键词: Sterically; Encumbered; Guanidinates; Kinetic; Stabilization

In this project, funded by the Chemical Synthesis Program of the Chemistry Division, Professor Skye Fortier of the Department of Chemistry at the University of Texas at El Paso (UTEP) is investigating the synthesis and reactivity of complexes that contain iron bound to nitrogen (iron nitrides). In both nature, and in industry, iron nitrides play a fleeting but critical role in capturing nitrogen from the air that we breathe and transferring it to important species (such as fertilizers for crop growth) ? a process known as nitrogen fixation. Despite the importance of iron nitrides in the global nitrogen fixation cycle (and in the marketplace), the study of molecules possessing individual iron nitride units has been hampered by the lack of model complexes. This project is developing new molecular architectures to access, trap, and study reactive iron nitride compounds. The goals are to shed light on the steps of the nitrogen fixation cycle and to use lessons learned to develop important, new nitrogen complexes using earth-abundant iron. Importantly, this chemistry utilizes iron which is a sustainable, non-toxic metal ? avoiding the need for costly and toxic precious metals. This project provides research opportunities for early-career scientists, including students from historically underrepresented groups. UTEP is a minority serving institution with an 80% Hispanic student population. The training and development the students receive is critically important for preparing the next generation of domestic science and technology personnel capable of competing in the global marketplace. On top of this, in an effort to encourage an active role in their learning, a student-directed seminar involves students in the hosting and organization of departmental seminars twice per semester. This program includes an ?Ask Me Anything? interview session where the students can learn from the life and professional experiences of the guest speaker as a professional development exercise and to reinforce resiliency and fortitude as traits for success. This project involves the use of "super bulky" guanidinate ligands to kinetically stabilize reactive iron-nitride compounds and delves into the factors that affect iron nitride reactivity. Using redox chemistry and ligand modifications, structure-function relationships are examined as they pertain to the electronics and chemical behavior of the iron-nitride moiety. A goal is to modulate the reactivity of the iron-nitride unit through ligand field effects, effectively using the ligand as a "chemical remote control" to influence the nucleophilicity/electrophilicity of the nitride group. A new professional development program at UTEP was initiated to better prepares the next generation of science and technology personnel. Students have an active and dynamic role in their education through the student-directed seminar program.

在这个项目中，由化学部的化学合成计划资助，德克萨斯大学埃尔帕索分校（UTEP）化学系的Skye Fortier教授正在研究含有与氮结合的铁（铁氮化物）的复合物的合成和反应性。 在自然界和工业中，氮化铁在从我们呼吸的空气中捕获氮并将其转移到重要物种（如作物生长的肥料）方面发挥着短暂但关键的作用。这一过程被称为固氮。尽管铁氮化物在全球固氮循环（和市场）中的重要性，但由于缺乏模型络合物，对具有单个铁氮化物单元的分子的研究受到阻碍。 该项目正在开发新的分子结构，以获取，捕获和研究反应性氮化铁化合物。 目标是阐明固氮循环的步骤，并利用所吸取的经验教训，利用地球丰富的铁开发重要的新氮复合物。重要的是，这种化学利用铁，这是一种可持续的，无毒的金属？避免了对昂贵和有毒的贵金属的需要。 该项目为早期职业科学家提供了研究机会，包括来自历史上代表性不足的群体的学生。UTEP是一个少数民族服务机构，80%的西班牙裔学生。学生接受的培训和发展对于培养下一代能够在全球市场上竞争的国内科技人员至关重要。最重要的是，为了鼓励学生在学习中发挥积极作用，学生指导的研讨会涉及学生每学期两次主办和组织部门研讨会。该计划包括一个？问我任何事？面试环节，学生可以从演讲嘉宾的生活和专业经验中学习，作为专业发展练习，并加强弹性和毅力作为成功的特质。该项目涉及使用“超大”胍基配体来动力学稳定反应性氮化铁化合物，并深入研究影响氮化铁反应性的因素。使用氧化还原化学和配体修饰，结构-功能关系进行检查，因为它们属于铁氮化物部分的电子和化学行为。目标是通过配体场效应调节铁-氮化物单元的反应性，有效地使用配体作为“化学远程控制”来影响氮化物基团的亲核性/亲电性。 UTEP启动了一项新的专业发展计划，以更好地培养下一代科技人员。 学生通过学生指导的研讨会计划在他们的教育中发挥积极和动态的作用。

项目成果

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H 2

双金属氮化钴 (III) 的分离及其氢原子抽象化学和 H 2 反应性的检测

• DOI: 10.1021/jacs.0c00291
• 发表时间: 2020
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Sengupta, Debabrata;Sandoval-Pauker, Christian;Schueller, Emily;Encerrado-Manriquez, Angela M.;Metta-Magaña, Alejandro;Lee, Wen-Yee;Seshadri, Ram;Pinter, Balazs;Fortier, Skye
• 通讯作者: Fortier, Skye

A Terminal Iron(IV) Nitride Supported by a Super Bulky Guanidinate Ligand and Examination of Its Electronic Structure and Reactivity

• DOI: 10.1021/jacs.7b06919
• 发表时间: 2017-11-08
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Maity, Arnab K.;Murillo, Jesse;Fortier, Skye
• 通讯作者: Fortier, Skye