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.

在该项目中，由化学部化学综合计划资助，得克萨斯大学El Paso（UTEP）化学系的Skye Fortier教授正在研究包含与氮结合的铁结合的复合物的合成和反应性（氮化铁）。 在自然界和工业中，氮化铁在捕获我们呼吸并将其转移到重要物种的空气中捕获氮（例如用于农作物生长的肥料）中起着短暂而关键的作用？一种称为氮固定的过程。尽管氮化铁在全球氮固定周期（以及市场）中的重要性，但缺乏模型复合物的缺乏，对拥有单个氮化铁单元的分子的研究受到了阻碍。 该项目正在开发新的分子体系结构，以获取，捕获和研究反应性氮化铁化合物。 目标是阐明氮固定周期的步骤，并使用学到的经验教训，使用含量丰富的铁开发重要的新氮配合物。重要的是，这种化学利用铁是一种可持续的无毒金属？避免需要昂贵和有毒的贵金属。 该项目为早期职业科学家提供了研究机会，包括历史上代表性不足的群体的学生。 UTEP是少数派服务机构，西班牙裔学生人数为80％。学生接受的培训和发展对于准备下一代能够在全球市场竞争的国内科学和技术人员至关重要。最重要的是，为了鼓励他们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持和组织部门研讨会。这个程序包括一个问我什么？面试会议，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，并增强韧性和毅力作为成功的特征。该项目涉及使用“超大”鸟甲酸糖配体来动力学稳定反应性硝酸铁化合物，并钻探到影响硝酸铁反应性的因素中。使用氧化还原化学和配体修饰，研究结构功能关系与氮化铁部分的电子和化学行为有关。一个目标是通过配体野外效应调节硝酸铁单元的反应性，有效地使用配体作为“化学遥控器”来影响硝酸盐基团的亲核性/亲电性。 启动了UTEP的一项新的专业发展计划，以更好地准备下一代科学和技术人员。 通过学生指导的研讨会计划，学生在教育中发挥了积极而充满活力的作用。

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