Bonding and Reactivity in Low-Valent Dinickel Complexes
低价二镍配合物中的键合和反应性
基本信息
- 批准号:1900035
- 负责人:
- 金额:$ 45.34万
- 依托单位:
- 依托单位国家:美国
- 项目类别:Standard Grant
- 财政年份:2019
- 资助国家:美国
- 起止时间:2019-07-01 至 2023-06-30
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
Bonding and Reactivity in Low-Valent Dinickel ComplexesA remarkable property of nickel compounds is their ability to break strong chemical bonds. Indeed, some proteins contain nickel centers that react with carbon dioxide, which has very strong bonds. Catalysts based on nickel are widely used in energy-related chemistry. The research project led by Professor Joseph P. Sadighi at the Georgia Institute of Technology builds on these themes of strong bonds and energy-relevance. The project focuses on pairs of nickel atoms. The nickel atoms are linked in pairs using bridging atoms or bridging groups. The linkers that are explored in this work include hydrogen, nonmetallic elements, or another metal. The project examines bridging centers that are weakly bonded to each nickel center. These unusually weak bonds should make the complexes sufficiently stable to be isolated, yet unstable enough to be highly reactive. A deeper understanding of these compounds is providing insights into the design of catalysts for breaking strong bonds. The graduate and undergraduate researchers who carry out this research are introduced to concepts of bonding and reactivity, and to an array of synthetic and spectroscopic techniques. The group also participates in a Georgia Tech program to recruit high school students from demographics underrepresented in science. The students are introduced to research through a summer and then through the academic year. This training prepares students to contribute to the future of science in the United States as teachers, or as researchers in academic, industrial, or government laboratories. The PI has extensive contacts with currently serving or recently transitioned veterans, and provides advice and encouragement to those returning to full-time study.Nickel has been the subject of remarkable recent advances in metal-element bonding, and in bond-breaking and bond-forming reactions that enable catalysis. This research presents architectures derived from the interaction of two nickel(0) centers with a Lewis acid to form a bridging ligand. When the Lewis acid is a proton, this interaction creates a rare linear hydride bridge; The [Ni---H---Ni]+ core is held together by a three-center, four-electron bond, analogous to that in the bifluoride ion. One aim is the synthesis of a series of related hydride-bridged dinickel complexes, enabling an assessment of the hydridic character of the bridging hydrogen, and a detailed study of the complex's reactivity toward the C-CN bonds of nitriles. Another aim explores the formation of bridges derived from Lewis-acidic main group species such as carbocations, boranes, alanes, or organometallic fragments. Finally, the insertion of copper(I) or gold(I) cations between the nickel centers would afford heterometallic systems with a single net bond across three metal centers. The hypothesis underpinning these aims is that the [Ni---E---Ni] ensembles are sufficiently stable for isolation or characterization, yet display reactivity distinct from that of mononickel complexes [Ni-E], nickel alone, or the bridging element alone. Students who work on this project learn concepts of bonding and chemical synthesis. They acquire technical skills in the preparation of air-sensitive complexes. They are trained in analysis using modern instrumentation. These researchers include graduate students, undergraduates, and high school students. The program identifies underrepresented minority students interested in scientific research. This training prepares students for technical careers in education, research, and industry. In another form of outreach, Professor Sadighi advises fellow veterans on their return to full-time study.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.
低价镍配合物中的成键和反应性镍化合物的一个显著特性是它们能够断开强化学键。事实上,一些蛋白质含有镍中心,与二氧化碳反应,二氧化碳具有非常强的键。基于镍的催化剂广泛用于与能源相关的化学。由格鲁吉亚理工学院的Joseph P. Sadighi教授领导的研究项目建立在这些强有力的联系和能源相关性的主题上。该项目的重点是镍原子对。镍原子使用桥接原子或桥接基团成对连接。在这项工作中探索的连接体包括氢,非金属元素或其他金属。该项目检查桥接中心,弱键合到每个镍中心。这些异常弱的键应该使复合物足够稳定以被分离,但又足够不稳定以具有高反应性。对这些化合物的更深入了解为设计用于破坏强键的催化剂提供了见解。进行这项研究的研究生和本科生研究人员介绍了键合和反应性的概念,以及一系列合成和光谱技术。该组织还参加了格鲁吉亚理工学院的一个项目,该项目旨在招募科学领域代表性不足的高中生。 学生们通过一个夏天,然后通过学年介绍研究。这种培训使学生能够作为教师或学术,工业或政府实验室的研究人员为美国科学的未来做出贡献。PI与目前在职或最近过渡的退伍军人有广泛的联系,并为那些返回全职学习的人提供建议和鼓励。镍一直是金属元素键合以及键断裂和键形成反应的最新进展的主题,这些反应使催化成为可能。本研究提出的架构来自两个镍(0)中心与刘易斯酸的相互作用,形成一个桥接配体。当刘易斯酸是质子时,这种相互作用产生了一个罕见的线性氢化物桥;[Ni-H-Ni]+核心通过一个三中心,四电子键结合在一起,类似于氟化氢离子。一个目的是合成一系列相关的cridde-bridged dinickel配合物,使评估的bridginghydrogen的cridgedic字符,并详细研究该配合物对腈的C-CN键的反应性。另一个目的是探索来自路易斯酸主族物质如碳阳离子、硼烷、铝烷或有机金属片段的桥的形成。最后,在镍中心之间插入铜(I)或金(I)阳离子将提供具有跨越三个金属中心的单一净键的异金属体系。支持这些目标的假设是,[Ni---E---Ni]系综对于分离或表征是足够稳定的,但显示出不同于单镍络合物[Ni-E]、单独的镍或单独的桥接元素的反应性。谁在这个项目工作的学生学习键和化学合成的概念。他们获得制备空气敏感复合物的技术技能。 他们接受使用现代仪器进行分析的培训。这些研究人员包括研究生、本科生和高中生。该计划确定了对科学研究感兴趣的少数民族学生。 这项培训为学生在教育,研究和工业中的技术职业做好准备。在另一种外展形式中,萨迪吉教授为退伍军人同胞重返全日制学习提供建议。该奖项反映了NSF的法定使命,并且通过使用基金会的知识价值和更广泛的影响审查标准进行评估,被认为值得支持。
项目成果
期刊论文数量(1)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Synthesis of a Nickel(I) alkoxide and related cation equivalents
- DOI:10.1016/j.poly.2021.115408
- 发表时间:2021-11
- 期刊:
- 影响因子:2.6
- 作者:Neil A. Dodd;J. Bacsa;J. Sadighi
- 通讯作者:Neil A. Dodd;J. Bacsa;J. Sadighi
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Joseph Sadighi其他文献
Joseph Sadighi的其他文献
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{{ truncateString('Joseph Sadighi', 18)}}的其他基金
N-Heterocyclic Carbenes in the Synthesis of Reactive Small Clusters of Group 11 Metals
N-杂环卡宾在第 11 族金属反应性小团簇合成中的应用
- 批准号:
1300659 - 财政年份:2013
- 资助金额:
$ 45.34万 - 项目类别:
Standard Grant
CAREER: Arene Functionalization by Metal Catalysts with Heavily Fluoronated Ligands
职业:通过金属催化剂与重氟化配体进行芳烃官能化
- 批准号:
0349204 - 财政年份:2004
- 资助金额:
$ 45.34万 - 项目类别:
Continuing Grant
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