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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

基本信息

批准号：
1654301
负责人：
Dmitry Peryshkov
金额：
$ 70.97万
依托单位：
University of South Carolina at Columbia
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：
2017-08-01 至 2023-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1654301&HistoricalAwards=false
关键词：
CAREER Carborane Cluster Architectures Featuring

项目摘要

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.

南卡罗来纳大学化学与生物化学系的Dmitry Peryshkov教授正在研究一种新型分子结构，这种结构可以在金属中心施加独特的电子和几何环境。该项目由化学系化学合成项目资助。这些结构，反过来，有望显著改变这些金属中心的化学反应性。一种不寻常的三维结构被称为碳硼烷，它由一簇硼和碳原子组成，用于合成这些具有新型化学键的金属配合物。本项目研究这些金属-硼键在有机分子活化和转化为有用产物中的作用。佩里什科夫博士还在制定一项推广计划，旨在促进南卡罗来纳州少数族裔群体的研究生水平教育和科学研究，其中包括传统黑人学院和大学的学生。该计划整合了无机和有机金属化学学生的教育和研究机会。在这个项目中，Peryshkov教授正在开发基于二十面体碳硼烷笼合成新型分子结构的方法。Peryshkov博士利用硼笼独特的三维几何形状和离域电子结构，在硼团簇表面形成金属中心的新型排列。碳硼烷、碳硼酰和碳硼烷键模式之间的快速相互转化对这些金属配合物的反应性起着重要作用，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)-碳炔配合物的合成方法，这是金属苯配合物的无机硼基类似物。这些碳炔不寻常的电子结构导致与有机和无机亲电成分的反应性增强。新型分子结构中金属-硼相互作用的研究为开发新的硼簇功能化合成方法及其在催化转化中的应用提供了基础认识。Peryshkov博士从事教育推广活动，旨在吸引和留住STEM学科的优秀学生，目标是属于代表性不足的少数群体的本科生。

项目成果

期刊论文数量（11）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

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.

Metal-Free Bond Activation by Carboranyl Diphosphines