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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.

在这个由化学部化学催化项目资助的项目中，亚利桑那州立大学的瑞安·特罗维奇（Ryan Trovitch）教授正在研究用丰富的金属（例如锰）制造催化剂的方法，这些金属可用于制备有机硅聚合物。聚合物是长链分子，其许多特性源自链之间的缠结和相互作用。聚合物已成为我们日常生活中无处不在的材料，影响着大多数行业，包括农业和食品、健康和安全以及交通运输。半个多世纪以来，有机硅聚合物已用于各种消费品，包括隐形眼镜、软管和医疗植入物。大多数广泛用于有机硅制备和固化的催化剂都是基于贵金属，例如铂或铱，这些元素的毒性相对较大，由于它们在地壳中的丰度较低，因此获取成本较高。用于有机硅制备的锰基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的重大进步。特罗维奇教授还致力于提高学生和公众对绿色化学的熟悉程度。他正在为当地高中生举办可持续发展研讨会，并将提供基于该计划的视频以实现广泛传播。作为绿色化学承诺的顾问委员会成员，他正在参与正在进行的举措，通过更新的课程和实验室经验向本科生和研究生介绍可持续化学的高级主题。特罗维奇教授还与凤凰城公共图书馆合作组织科学咖啡馆讨论。在该项目中，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硅烷化催化剂，该催化剂将表现出与广泛使用的贵金属催化剂相当的活性和选择性。相对于第二和第三行过渡金属，锰由于倾向于参与单电子反应途径，因此在催化应用中仍未得到充分利用。最近的结果表明，多齿、氧化还原非无害螯合配体通过在整个催化过程中可逆地转移电子和部分解离来实现锰催化的羰基氢化硅烷化。基于这一发现，Trovitch 教授正在研究锰催化的硅氢加成反应的多个方面，包括可替代铂基硅氢加成催化剂的锰烯烃硅氢加成催化剂、用于交联聚酮与聚氢硅烷或聚氢硅氧烷的新型羰基硅氢加成途径，以及合成的脱氢甲硅烷基化途径。硅氧烷网络。通过电子结构测定和机理研究，通过明智地修改其配体框架，开发用于烯烃氢化硅烷化、羰基氢化硅烷化和脱氢硅烷化的高活性锰催化剂。该项目的成功完成将改变锰催化的现有知识，同时揭示高密度氧化还原非无害螯合物利用的潜在优势。

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.

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.

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

Hydrosilylation of Aldehydes and Formates Using a Dimeric Manganese Precatalyst

使用二聚锰预催化剂进行醛和甲酸酯的氢化硅烷化

DOI：
10.1021/acs.organomet.7b00423
发表时间：
2017
期刊：
Organometallics
影响因子：
2.8
作者：
Mukhopadhyay, Tufan K.;Ghosh, Chandrani;Flores, Marco;Groy, Thomas L.;Trovitch, Ryan J.
通讯作者：
Trovitch, Ryan J.