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Fundamental reactivity of PtII/PtIV redox couple relevant to oxidative alkane C-H bond functionalization with O2 as direct oxidant

PtII/PtIV 氧化还原对与 O2 作为直接氧化剂氧化烷烃 C-H 键功能化相关的基本反应性

基本信息

批准号：
1464772
负责人：
Andrei Vedernikov
金额：
$ 47万
依托单位：
University of Maryland, College Park
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2015
资助国家：
美国
起止时间：
2015-08-01 至 2019-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1464772&HistoricalAwards=false
关键词：
Fundamental reactivity PtII PtIV redox

项目摘要

With this award, the Chemical Synthesis Program of the Chemistry Division is funding Professor Andrei N. Vedernikov of the University of Maryland to develop new catalysts for converting compounds typically abundant in natural gas, i.e unreactive hydrocarbons into functionalized compounds with added value. Importantly, this 'green' project proposes to use oxygen from the air as the only consumable reagent for the desired oxidative transformations. To accomplish the goal, computational design is combined with experimental study of the reactions involved. To enhance the chances for success the project includes collaboration with the theoretical computational group of Professor William A. Goddard, III from Caltech. The broader impacts include the training of students via the ACS Project SEED Program from area high schools through participation in this research.This project aims at a detailed mechanistic understanding of how facially chelating ligands control reactivity of a Pt center in alkane C-H bond activation. These studies follow on earlier work in Professor Vedernikov's group on Pt(II)species that mediate aerobic functionalization of C-H bonds. Several series of novel Pt(II) complexes are being developed, including sulfonated CNN pincer complexes and macrocyclic pyridinophane complexes. This work includes DFT (Density Functional Theory)-driven catalyst discovery and detailed mechanistic characterization of new systems by means of kinetics, isotopic labeling experiments and DFT calculations. If successful, some of the new systems may serve as efficient catalysts for partial aerobic oxidation of methane and higher alkanes.

有了这个奖项，化学系的化学合成计划资助教授安德烈N。与马里兰州大学的Vedernikov合作，开发新的催化剂，用于将天然气中通常富含的化合物，即不反应的烃转化为具有附加值的官能化化合物。重要的是，这个“绿色”项目提出使用空气中的氧气作为所需氧化转化的唯一消耗试剂。为了实现这一目标，计算设计与所涉及的反应的实验研究相结合。为了提高成功的机会，该项目包括与威廉A。加州理工学院的戈达德三世更广泛的影响包括通过参与本研究，通过ACS项目SEED计划对来自地区高中的学生进行培训。该项目旨在详细了解表面螯合配体如何控制烷烃C-H键活化中Pt中心的反应性。这些研究是在Vedernikov教授小组关于介导C-H键有氧官能化的Pt（II）物种的早期工作之后进行的。目前正在开发几个系列的新型Pt（II）配合物，包括磺化CNN钳形配合物和大环吡啶并噻吩配合物。这项工作包括DFT（密度泛函理论）驱动的催化剂发现和详细的机制表征的新系统的动力学，同位素标记实验和DFT计算。如果成功的话，一些新的系统可以作为甲烷和高级烷烃的部分有氧氧化的有效催化剂。