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Susan A. Nye

Bio: Susan A. Nye is an academic researcher from Momentive. The author has contributed to research in topics: Hydrosilylation & Cobalt. The author has an hindex of 10, co-authored 21 publications receiving 881 citations.

Papers
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Journal ArticleDOI
03 Feb 2012-Science
TL;DR: It is reported that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions, showing promise for industrial application.
Abstract: Alkene hydrosilylation, the addition of a silicon hydride (Si-H) across a carbon-carbon double bond, is one of the largest-scale industrial applications of homogeneous catalysis and is used in the commercial production of numerous consumer goods. For decades, precious metals, principally compounds of platinum and rhodium, have been used as catalysts for this reaction class. Despite their widespread application, limitations such as high and volatile catalyst costs and competing side reactions have persisted. Here, we report that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions. These Earth-abundant base-metal catalysts, coordinated by optimized bis(imino)pyridine ligands, show promise for industrial application.

444 citations

Journal ArticleDOI
TL;DR: The aryl-substituted bis(imino)pyridine cobalt methyl complex, ((Mes)PDI)CoCH3), promotes the catalytic dehydrogenative silylation of linear α-olefins to selectively form the corresponding allylsilanes with commercially relevant tertiary silanes such as (Me3SiO)2MeSiH and (EtO)3SiH.
Abstract: The aryl-substituted bis(imino)pyridine cobalt methyl complex, (MesPDI)CoCH3 (MesPDI = 2,6-(2,4,6-Me3C6H2-N═CMe)2C5H3N), promotes the catalytic dehydrogenative silylation of linear α-olefins to selectively form the corresponding allylsilanes with commercially relevant tertiary silanes such as (Me3SiO)2MeSiH and (EtO)3SiH. Dehydrogenative silylation of internal olefins such as cis- and trans-4-octene also exclusively produces the allylsilane with the silicon located at the terminus of the hydrocarbon chain, resulting in a highly selective base-metal-catalyzed method for the remote functionalization of C–H bonds with retention of unsaturation. The cobalt-catalyzed reactions also enable inexpensive α-olefins to serve as functional equivalents of the more valuable α, ω-dienes and offer a unique method for the cross-linking of silicone fluids with well-defined carbon spacers. Stoichiometric experiments and deuterium labeling studies support activation of the cobalt alkyl precursor to form a putative cobalt sil...

171 citations

Journal ArticleDOI
TL;DR: In this article, three different classes of tridentate, nitrogen-based, terpyridine, and pyridine bis(oxazoline) ligands have been synthesized and evaluated in the catalytic hydrosilylation of olefins with tertiary silanes.

128 citations

Journal ArticleDOI
TL;DR: Aryl-substituted bis(imino)pyridine iron dinitrogen complexes are active for the hydrosilylation of 1,2,4-trivinylcyclohexane with tertiary alkoxy silanes, a process used in the manufacture of low rolling resistance tires as discussed by the authors.
Abstract: Aryl-substituted bis(imino)pyridine iron dinitrogen complexes are active for the hydrosilylation of 1,2,4-trivinylcyclohexane with tertiary alkoxy silanes, a process used in the manufacture of low rolling resistance tires. The iron compounds exhibit unprecedented selectivity for the monohydrosilylation of the desired 4-alkene that far exceeds results obtained with commercially used platinum compounds.

113 citations

Patent
22 Nov 2011
TL;DR: In this article, a process for the hydrosilylation of a composition containing a silyl hydride and a compound containing at least one unsaturated group is described, the process comprising contacting a non-previous metal based complex as a catalyst precursor with an activator being a reducing agent.
Abstract: Disclosed herein is a process for the hydrosilylation of a composition containing a silyl hydride and a compound containing at least one unsaturated group, the process comprising contacting a non-previous metal based complex as a catalyst precursor with an activator being a reducing agent shortly before, simultaneously or after contacting the complex with the composition, to cause the silyl hydride to react with the compound containing at least one unsaturated group to produce a hydrosilylation product.

19 citations


Cited by
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Journal ArticleDOI
29 Nov 2013-Science
TL;DR: In this paper, the authors report convenient and stable iron oxide (Fe2O3)-based catalysts as a more earth-abundant alternative for the transformation of anilines.
Abstract: Production of anilines--key intermediates for the fine chemical, agrochemical, and pharmaceutical industries--relies on precious metal catalysts that selectively hydrogenate aryl nitro groups in the presence of other easily reducible functionalities. Herein, we report convenient and stable iron oxide (Fe2O3)-based catalysts as a more earth-abundant alternative for this transformation. Pyrolysis of iron-phenanthroline complexes on carbon furnishes a unique structure in which the active Fe2O3 particles are surrounded by a nitrogen-doped carbon layer. Highly selective hydrogenation of numerous structurally diverse nitroarenes (more than 80 examples) proceeded in good to excellent yield under industrially viable conditions.

800 citations

Journal ArticleDOI
TL;DR: A mechanistic framework for understanding this compendium of radical reactions is provided, covering the development of the field and contributions to reaction invention, mechanism, and application to complex molecule synthesis.
Abstract: Cofactor-mimetic aerobic oxidation has conceptually merged with catalysis of syngas reactions to form a wide range of Markovnikov-selective olefin radical hydrofunctionalizations. We cover the development of the field and review contributions to reaction invention, mechanism, and application to complex molecule synthesis. We also provide a mechanistic framework for understanding this compendium of radical reactions.

553 citations

Journal ArticleDOI
TL;DR: This review aims at providing a comprehensive picture of the utilization of functional pincer ligands in first-row transition metal hydrogenation and dehydrogenation catalysis and related synthetic concepts relying on these such as the hydrogen borrowing methodology.
Abstract: The use of 3d metals in de/hydrogenation catalysis has emerged as a competitive field with respect to “traditional” precious metal catalyzed transformations. The introduction of functional pincer ligands that can store protons and/or electrons as expressed by metal–ligand cooperativity and ligand redox-activity strongly stimulated this development as a conceptual starting point for rational catalyst design. This review aims at providing a comprehensive picture of the utilization of functional pincer ligands in first-row transition metal hydrogenation and dehydrogenation catalysis and related synthetic concepts relying on these such as the hydrogen borrowing methodology. Particular emphasis is put on the implementation and relevance of cooperating and redox-active pincer ligands within the mechanistic scenarios.

502 citations

Journal ArticleDOI
27 Apr 2018
TL;DR: Transition-metal-catalysed hydrosilylation and hydroboration reactions are valuable in the synthesis of commodity and fine chemicals, respectively and the catalyst design principles that enable us to perform these reactions using catalysts based on earth-abundant metals are described.
Abstract: The addition of a silicon-hydrogen or a boron-hydrogen bond across a carbon-carbon multiple bonds is a well-established method for the introduction of versatile silane and borane functional groups to base hydrocarbon feedstocks. Transition metal catalysis, historically with precious second- and third- row transition metals, has been used to broaden the scope of the hydrofunctionalization reaction, improve reaction rate and enhance selectivity. The anti-Markovnikov selectivity of platinum-catalyzed hydrosilylation of alkenes, for example, is an enabling synthetic technology in the multibillion-dollar silicones industry. Increased emphasis on sustainable catalytic methods and more economic processes has shifted focus to catalysis with more earth-abundant transition metals such as iron, cobalt and nickel. This review describes contemporary approaches and offers a contextual analysis of catalytic alkene hydrosilylation and hydroboration reactions using first-row transition metals. Emphasis is placed on defining advances in the field, what constitutes catalyst cost, safety, and important design features to enable precious metal-like reactivity, as well as new chemistry that is unique to first-row transition metals.

495 citations