Microwave Measurements of Structures and Electronic Properties of Transition Metal Complexes, Hydrogen-Bonded Complexes, and Radicals

过渡金属配合物、氢键配合物和自由基的结构和电子性质的微波测量

• 批准号: 1057796
• 负责人: Stephen Kukolich
• 金额: $ 40万
• 依托单位: University of Arizona
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-09-01 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1057796&HistoricalAwards=false
• 关键词: Microwave; Measurements; Structures; Electronic; Properties

With this award from the Chemical Structure, Dynamics and Mechanisms program, Professor Stephen Kukolich of the University of Arizona will modify and use pulsed-beam, Fourier-transform microwave spectrometers to measure rotational transition frequencies in the 1 to 18 GHz region of the microwave spectrum. The completion of a new 1-10 GHz, spectrometer provides an unusual capability for measuring lower frequency transitions of larger molecules and complexes. A laser-photodissociation beam source will be used for measurements on organometallic radicals and their reaction products. The overall objectives of this work include measurements of the three-dimensional gas-phase structures, quadrupole coupling strengths and magnetic interaction parameters. These measurements are proposed for: a) mononuclear and dinuclear transition metal complexes, b) weakly-bound complexes involving transition metals, c) hydrogen-bonded complexes and d) transition metal radicals. The quadrupole coupling strengths and magnetic interaction parameters directly characterize the electronic charge distributions. Quantum mechanical (DFT or mp2) calculations will be carried out for all of the complexes studied. The coordination of experimental work with the theoretical calculations helps to make the measurements more efficient, improves our understanding of the electronic structure of molecules and provides guidelines and experimental examples for improvements in ab initio, quantum chemistry calculations. Transition metal complexes are very important in the chemical industry, in biological systems and as an area of study in inorganic chemistry. Millions of tons of chemical products are produced each year using reactions which involve transition metal catalysts. The active sites of many enzymes and transport proteins in living systems contain transition metal complexes. A large fraction of the research and study in inorganic chemistry is focused on transition metal complexes, and the proposed work will provide new contributions to the structural database that is used in research, industry and education. The proposed work will often involve smaller, "model" complexes, but will provide results relevant to the larger, more complex systems. The accurate, three-dimensional structures for transition metal complexes, are helpful in understanding reaction mechanisms. Successful modeling of reaction mechanisms in chemistry and biology often depends on the accurate and reliable experimental structural information. Improving calculation methods and basis sets through correlation with new experimental data is useful because the calculations are presently the only source of detailed information on short-lived radicals or high-energy reaction intermediates. Studies of metal dihydrogen complexes may provide information which will be useful for improving hydrogen storage technology. Graduate and undergraduate research students will learn fundamentals of chemistry, quantum mechanics and methods and techniques involved in computer work, microwave electronics and making physical measurements through direct involvement in the proposed projects. Participation in the research by underrepresented minorities and secondary school teachers, or non-Ph.D. college students will be actively sought for the proposed projects.

凭借化学结构，动力学和机制计划的这一奖项，亚利桑那大学的Stephen Kukolich教授将修改和使用脉冲束傅里叶变换微波光谱仪来测量微波频谱1至18 GHz区域的旋转跃迁频率。 新的1-10 GHz光谱仪的完成为测量较大分子和复合物的低频跃迁提供了不寻常的能力。 激光光解离光束源将用于测量有机金属自由基及其反应产物。 这项工作的总体目标包括三维气相结构，四极耦合强度和磁相互作用参数的测量。 这些测量被提议用于：a）单核和双核过渡金属配合物，B）涉及过渡金属的弱结合配合物，c）氢键配合物和d）过渡金属自由基。 四极耦合强度和磁相互作用参数直接表征了电子的电荷分布。 量子力学（DFT或mp2）计算将进行所有的研究复合物。 实验工作与理论计算的协调有助于使测量更有效，提高我们对分子电子结构的理解，并为从头算，量子化学计算的改进提供指导方针和实验实例。 过渡金属配合物在化学工业、生物体系和无机化学的研究领域中非常重要。 每年使用涉及过渡金属催化剂的反应生产数百万吨化学产品。 生命系统中许多酶和转运蛋白的活性部位都含有过渡金属配合物。 无机化学的研究和研究的很大一部分集中在过渡金属配合物上，拟议的工作将为研究，工业和教育中使用的结构数据库提供新的贡献。 拟议的工作往往涉及较小的“模型”复合体，但将提供与较大的、更复杂的系统相关的结果。 过渡金属配合物精确的三维结构有助于理解反应机理。 化学和生物学中反应机理的成功建模往往依赖于准确可靠的实验结构信息。 通过与新的实验数据相关来改进计算方法和基组是有用的，因为计算是目前关于短寿命自由基或高能反应中间体的详细信息的唯一来源。 金属二氢配合物的研究可为改进储氢技术提供有用的信息。 研究生和本科研究生将学习化学，量子力学和方法的基础知识和计算机工作，微波电子学和通过直接参与拟议的项目进行物理测量所涉及的技术。 参与研究的人数不足的少数民族和中学教师，或非博士将积极争取大学生参与建议的项目。

项目成果

Microwave measurements of rotational transitions and nitrogen quadrupole coupling for 2-aminopyridine

2-氨基吡啶旋转跃迁和氮四极耦合的微波测量

• 发表时间: 2021
• 期刊: Journal of molecular spectroscopy
• 影响因子: 1.4
• 作者: Zunwu, Z.;Daly, A.;Kukolich, S.
• 通讯作者: Kukolich, S.

Corrections and Additions to “Microwave Spectra and Theoretical Calculations for Two Structural Isomers of Methylmanganese Pentacarbonyl”

对“五羰基甲基锰的两种结构异构体的微波光谱和理论计算”的修正和补充

• DOI: 10.1021/acs.inorgchem.0c03388
• 发表时间: 2021
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Tanjaroon, Chakree;Zhou, Zunwu;Mills, David;Keck, Kristen;Kukolich, Stephen G.
• 通讯作者: Kukolich, Stephen G.

Calculations and analysis of 55Mn nuclear quadrupole coupling for asymmetric top acyl methyl manganese pentacarbonyl

不对称顶酰基甲基五羰基锰的55Mn核四极耦合计算与分析

• 发表时间: 2021
• 期刊: Chemical physics letters
• 影响因子: 2.8
• 作者: Tanjaroon, C;Mills, D.;Jiménez Hoyos, C.;Kukolich, S.
• 通讯作者: Kukolich, S.

Microwave spectra and theoretical calculations for two structural isomers of methylmanganese pentacarbonyl

五羰基甲基锰的两种结构异构体的微波谱及理论计算

• DOI: 10.1021/acs.inorgchem.0c00524
• 发表时间: 2020
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Tanjaroon, C.;Zhou, Z.;Mills, D.;Keck, K.;Kukolich, S.
• 通讯作者: Kukolich, S.