CAREER: SusChEM: Development of Manganese Hydrosilylation Catalysts for Silicone Curing

职业：SusChEM：开发用于有机硅固化的锰硅氢加成催化剂

基本信息

批准号：
1651686
负责人：
Ryan Trovitch
金额：
$ 65万
依托单位：
Arizona State University
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：
2017-06-01 至 2023-05-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1651686&HistoricalAwards=false
关键词：
CAREER SusChEM Development Manganese Hydrosilylation

项目摘要

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Ryan Trovitch of Arizona State University is studying ways to make catalysts from abundant metals, such as manganese, that can be used to prepare silicone polymers. Polymers are long chain molecules that derive many of their properties from the entanglements and interactions between the chains. Polymers have become ubiquitous materials in our daily lives, impacting most industries, including agriculture and food, health and safety, as well as transportation. For more than half a century, silicone polymers have been used in a variety of consumer products including contact lenses, flexible tubing, and medical implants. Most catalysts that are widely employed in silicone preparation and curing are based on precious metals such as platinum or iridium, relatively toxic elements that are costly to obtain due to their low abundance in the Earth's crust. The development of manganese-based catalysts for silicone preparation would have the potential to supplant precious metal catalyst use, which would represent a significant advance in sustainable chemistry. Professor Trovitch is also working to enhance student and public familiarity with green chemistry. He is developing a sustainability workshop for local high school students, and videos based upon this program will be made available to achieve broad dissemination. As an Advisory Board Member of the Green Chemistry Commitment, he is participating in ongoing initiatives to introduce undergraduate and graduate students to advanced topics in sustainable chemistry through updated coursework and laboratory experiences. Professor Trovitch is also organizing Science Cafe discussions in collaboration with the Phoenix Public Library. In this project, Prof. Ryan J. Trovitch of Arizona State University is developing sustainable manganese hydrosilylation catalysts that will exhibit comparable activity and selectivity to widely used precious metal catalysts. Relative to second and third row transition metals, manganese remains underutilized in catalytic applications due to its propensity to participate in one-electron reaction pathways. Recent results have shown that polydentate, redox non-innocent chelate ligands enable manganese-catalyzed carbonyl hydrosilylation by reversibly transferring electrons and partially dissociating throughout catalysis. Building on this discovery, Professor Trovitch is studying several aspects of manganese-catalyzed hydrosilylation reactions including manganese olefin hydrosilylation catalysts that can serve as replacements for ones based upon platinum, novel carbonyl hydrosilylation pathways to crosslink polyones with polyhydrosilanes or polyhydrosiloxanes, and dehydrogenative silylation pathways to the synthesis of siloxane networks. Via electronic structure determinations and mechanistic studies, highly active manganese catalysts for olefin hydrosilylation, carbonyl hydrosilylation, and dehydrogenative silylation are being developed by judiciously modifying their ligand frameworks. Successful completion of this project will transform current knowledge of manganese catalysis while revealing potential advantages of high-denticity redox non-innocent chelate utilization.

在化学部化学催化计划资助的该项目中，亚利桑那州立大学的瑞安·特罗维奇（Ryan Trovitch）教授正在研究制造来自大量金属（例如锰）的催化剂，可用于制备硅胶聚合物。聚合物是长链分子，它们从链之间的纠缠和相互作用中得出许多特性。聚合物已成为我们日常生活中无处不在的材料，影响了大多数行业，包括农业和食品，健康与安全以及运输。在半个多世纪的时间里，有机硅聚合物已用于多种消费产品，包括隐形眼镜，柔性管和医用植入物。大多数在硅酮制备和固化中广泛使用的催化剂都是基于贵金属，例如铂或虹膜，相对毒性的元素，由于它们在地壳中的丰度低而获得的昂贵。用于硅胶制备的基于锰的催化剂的开发将有可能取代贵金属催化剂的使用，这将代表可持续化学方面的重大进步。 Trovitch教授还在努力增强学生和公众对绿色化学的熟悉。他正在为当地高中生开发一个可持续性研讨会，并且将根据该计划进行视频，以实现广泛的传播。作为绿色化学承诺的顾问委员会成员，他通过更新的课程和实验室经验，参与正在进行的倡议，将本科生和研究生引入可持续化学的高级主题。 Trovitch教授还与凤凰公共图书馆合作组织了科学咖啡馆讨论。在这个项目中，亚利桑那州立大学的Ryan J. Trovitch教授正在开发可持续的锰氢化催化剂，该催化剂将表现出可比性的活性和对广泛使用的贵金属催化剂的可比性。相对于第二排和第三排过渡金属，锰由于参与单电子反应途径的倾向而在催化施用中仍未得到充分利用。最近的结果表明，氧化氧化还原的非处以螯合配体可以通过可逆地转移电子并在整个催化过程中部分解离，从而使锰催化的羰基氢硅烷基化。基于这一发现，Trovitch教授正在研究锰催化的氢硅烷二硅烷基化反应的几个方面，包括锰烯烃的水硅烷基催化剂，可以用作基于铂的新型羰基水硅烷基水硅烷基于与多羟基烷酸盐的多脑链接式多源的链氨甲基链接途径的新型羰基水硅烷基途径的替代品的替代品，并且硅氧烷网络的合成。通过电子结构的确定和机理研究，通过明智地通过明智地修改其配体框架来开发高度活性的锰催化剂，用于烯烃氢硅烷化，羰基氢硅酮和脱氢作用。该项目的成功完成将改变当前对锰催化的知识，同时揭示出高道氧化物氧化还原非一般性螯合物利用率的潜在优势。

项目成果

期刊论文数量（13）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

The electronic structure of a β-diketiminate manganese hydride dimer

β-二酮亚胺氢化锰二聚体的电子结构

DOI：
10.1039/d0dt02842h
发表时间：
2020
期刊：
Dalton Transactions
影响因子：
4
作者：
Oh, Changjin;Siewe, Joëlle;Nguyen, Thao T.;Kawamura, Airi;Flores, Marco;Groy, Thomas L.;Anderson, John S.;Trovitch, Ryan J.;Baik, Mu-Hyun
通讯作者：
Baik, Mu-Hyun

Efficient Cobalt Catalyst for Ambient-Temperature Nitrile Dihydroboration, the Elucidation of a Chelate-Assisted Borylation Mechanism, and a New Synthetic Route to Amides

DOI：
10.1021/jacs.9b07529
发表时间：
2019-09-25
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子：
15
作者：
Ghosh, Chandrani;Kim, Suyeon;Trovitch, Ryan J.
通讯作者：
Trovitch, Ryan J.

Comparing the Electronic Structure of Iron, Cobalt, and Nickel Compounds That Feature a Phosphine-Substituted Bis(imino)pyridine Chelate

比较具有膦取代双（亚氨基）吡啶螯合物的铁、钴和镍化合物的电子结构

DOI：
10.1021/acs.inorgchem.2c00008
发表时间：
2022
期刊：
Inorganic Chemistry
影响因子：
4.6
作者：
Mena, Matthew R.;Kim, Jun-Hyeong;So, Sangho;Ben-Daat, Hagit;Porter, Tyler M.;Ghosh, Chandrani;Sharma, Anuja;Flores, Marco;Groy, Thomas L.;Baik, Mu-Hyun
通讯作者：
Baik, Mu-Hyun

An aryl diimine cobalt( i ) catalyst for carbonyl hydrosilylation

用于羰基硅氢加成的芳基二亚胺钴(i)催化剂

DOI：
10.1039/d2cc04089a
发表时间：
2022
期刊：
Chemical Communications
影响因子：
4.9
作者：
Sharma, Anuja;So, Sangho;Kim, Jun-Hyeong;MacMillan, Samantha N.;Baik, Mu-Hyun;Trovitch, Ryan J.
通讯作者：
Trovitch, Ryan J.

Isolation of Mn(I) Compounds Featuring a Reduced Bis(imino)pyridine Chelate and Their Relevance to Electrocatalytic Hydrogen Production

具有还原双（亚氨基）吡啶螯合物的 Mn(I) 化合物的分离及其与电催化制氢的相关性

DOI：
10.1021/acs.inorgchem.8b00588
发表时间：
2018
期刊：
Inorganic Chemistry
影响因子：
4.6
作者：
Mukhopadhyay, Tufan K.;MacLean, Nicholas L.;Flores, Marco;Groy, Thomas L.;Trovitch, Ryan J.
通讯作者：
Trovitch, Ryan J.