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CAREER: Carborane Cluster Architectures Featuring Multiple Metal-Boron Interactions

CAREER: Carborane Cluster Architectures Featuring Multiple Metal-Boron Interactions
职业:具有多种金属-硼相互作用的碳硼烷簇结构
批准号:
1654301
负责人:
Dmitry Peryshkov
金额:
$70.97万
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
项目状态:
已结题
起止时间:
2017-08-01 至 2023-07-31

项目摘要

项目成果

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中文摘要
翻译
职业生涯:具有多种金属-硼相互作用的Carborane簇体系结构在这个由化学系化学合成计划资助的项目中,南卡罗来纳大学化学和生物化学系的Dmitry Peryshkov教授正在开发新的分子体系结构,在金属中心实施独特的电子和几何环境。反过来,这些结构有望显著改变这些金属中心的化学反应活性。一种被称为碳硼烷的不寻常的三维结构,由一簇硼和碳原子组成,被用来合成这些具有新的化学键的金属络合物。这个项目研究了这些金属-硼键在有机分子活化和转化为有用产品中的作用。佩里什科夫博士还在制定一项外展计划,在南卡罗来纳州代表性不足的少数族裔群体中推广研究生水平的教育和科学研究,其中包括历史悠久的黑人学院和大学的学生。该项目为学生提供了无机和有机金属化学方面的教育和研究机会。在这个项目中,Peryshkov教授正在开发基于二十面体碳硼烷笼子的新型分子结构的合成方法。佩里什科夫博士利用硼笼独特的三维几何结构和离域电子结构,在硼团簇表面获得了新型的金属中心排列。Carborane、Carboranyl和Carboryne成键方式之间的相互转化在这些金属配合物的反应活性中起着重要作用,并导致有机底物的协同活化。Peryshkov博士还在开发含有三元(B)(B)(M)金属环的新型(BB)-Carboryne配合物的合成方法,这是一种基于无机硼的金属苯配合物的类似物。这些碳氢化合物的特殊电子结构导致与有机和无机亲电组分的反应性增强。对新型分子结构中金属-硼相互作用的研究为开发新的合成方法来实现硼原子簇的功能化及其在催化转化中的应用提供了基本的认识。佩里什科夫博士参与了旨在吸引和留住STEM学科有才华的学生的教育推广倡议,目标是属于代表性不足的少数群体的本科生。
英文摘要
CAREER: Carborane Cluster Architectures Featuring Multiple Metal-Boron InteractionsIn this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Dmitry Peryshkov of the Department of Chemistry and Biochemistry at the University of South Carolina is developing novel molecular architectures that enforce unique electronic and geometric environments on metal centers. These architectures, in turn, are expected to significantly change the chemical reactivity of these metal centers. An unusual three-dimensional structure known as a carborane, which consists of a cluster of boron and carbon atoms, is utilized for the synthesis of these metal complexes with novel chemical bonds. This project studies the role of these metal-boron bonds in the activation and transformation of organic molecules into useful products. Dr. Peryshkov is also developing an outreach initiative, which promotes graduate-level education and scientific research among underrepresented minority groups in South Carolina, including students at Historically Black Colleges and Universities. This program integrates educational and research opportunities for students in inorganic and organometallic chemistry.In this project, Professor Peryshkov is developing methods to synthesize novel molecular architectures based on icosahedral carborane cages. Dr. Peryshkov utilizes the unique three-dimensional geometry and delocalized electronic structure of boron cages to access novel types of arrangements of metal centers on the surfaces of boron clusters. Facile interconversion between carborane, carboranyl, and carboryne bonding modes plays an important role in the reactivity of these metal complexes and leads to cooperative activation of organic substrates. Dr. Peryshkov is also developing synthetic methods for novel (BB)-carboryne complexes containing three-membered (B)(B)(M) metallacycles, which are inorganic boron-based analogs of metal benzyne complexes. The unusual electronic structure of these carborynes results in enhanced reactivity with organic and inorganic electrophilic components. Studies of metal-boron interactions in the novel molecular architectures provide a fundamental understanding for development of new synthetic approaches to functionalization of boron clusters and their utilization in catalytic transformations. Dr. Peryshkov is engaged in the educational outreach initiative aimed to attract and retain talented students in STEM disciplines targeting undergraduate students belonging to underrepresented minority groups.
期刊论文(11)
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会议论文
Room-Temperature Aerobic C–CN Bond Activation in Nickel(II) Cyanomethyl Dicarboranyl Complex
镍(II)氰甲基二碳硼基络合物中的室温需氧 C–CN 键活化
DOI: 10.1021/acs.organomet.3c00216
发表时间: 2023
期刊: Organometallics
影响因子: 2.8
作者: [Islam, Mohammad Jahirul, Park, Kyoung Chul, Manley, Olivia M., Smith, Mark D., Makris, Thomas M., Peryshkov, Dmitry V.]
通讯作者: Peryshkov, Dmitry V.
DOI: 10.1021/jacs.1c05387
发表时间: 2021-07-13
期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子: 15
作者: [Gange, Gayathri B., Humphries, Amanda L., Peryshkov, Dmitry, V]
通讯作者: Peryshkov, Dmitry, V
DOI: 10.1016/j.tet.2019.02.010
发表时间: 2019-03-15
期刊: TETRAHEDRON
影响因子: 2.1
作者: [Eleazer, Bennett J., Smith, Mark D., Peryshkov, Dmitry, V]
通讯作者: Peryshkov, Dmitry, V
Imido Group Interchange in Reactions of Zwitterionic Tantalum(V) Vinylimido Complexes and Nitriles
两性离子钽(V)乙烯基酰亚胺配合物与腈反应中的亚氨基交换
DOI: 10.1021/acs.organomet.8b00241
发表时间: 2018
期刊: Organometallics
影响因子: 2.8
作者: [Rahman, Md. Mamdudur, Smith, Mark D., Peryshkov, Dmitry V.]
通讯作者: Peryshkov, Dmitry V.
Redox-Active Carborane Clusters for Metal-Free Bond Activation
海外基金