Maurice Brookhart

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Maurice Brookhart
Brookhart Maurice.jpg
Born(1942-11-28)November 28, 1942
Citizenship United States
Alma mater Johns Hopkins,
UCLA
Known forMechanisms in organometallic chemistry
Agostic interaction
Brookhart's acid
Brookhart's catalysts
Awards Oesper Award (2016)
Willard Gibbs Award (2010)
North Carolina Award(2008)
Centenary Prize (2000)
Scientific career
Fields Organometallic chemistry
Institutions University of Houston 2015–present
University of North Carolina at Chapel Hill 1969–2015
Doctoral advisor Saul Winstein

Maurice S. Brookhart (born 1942) is an American chemist, and professor of chemistry at the University of Houston since 2015.

Brookhart received his bachelor's degree from Johns Hopkins University in 1964. He received his PhD in 1968 from the University of California, Los Angeles, in physical organic chemistry where his thesis advisor was Saul Winstein. [2] [3] [4] [5] After an NSF postdoctoral fellowship at the University of California, Los Angeles in 1968 and a NATO postdoctoral fellowship at Southampton University, England. In 1969, he joined the faculty of the University of North Carolina, where he stayed until 2015, when he joined the University of Houston as a professor of chemistry.

His research group is noted for its research in the general area of synthetic and mechanistic organometallic chemistry. A recent major thrust has been the development of post-metallocene catalysts based upon late transition metal (Ni and Pd) complexes for olefin coordination polymerization. [6] [7] [8] They carry out their mechanistic investigation of the polymerization reactions primarily by low temperature IR and NMR spectroscopies. The work provides a detailed understanding of catalyst resting states and relative intermediates.

A second major focus of Brookhart's group concerns fundamental studies of C-H [9] and C-C bond activations by transition metal complexes and the incorporation of these bond activation steps into catalytic cycles. They have successfully demonstrated catalysis of the ortho-alkylation of aromatic ketones, alkyl aldehyde isomerization, hydroacylation, and the dehydrogenation of alkoxy silanes to generate silyl enol ethers. [10] Recent work on alkane metathesis has received attention. [11] [12]

He has over 300 publications in the scientific literature and holds over 22 US patents. He is a member of the National Academy of Sciences.

Related Research Articles

<span class="mw-page-title-main">Alkene</span> Hydrocarbon compound containing one or more C=C bonds

In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond.

<span class="mw-page-title-main">Organometallic chemistry</span> Study of organic compounds containing metal(s)

Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.

In chemistry, dehydrogenation is a chemical reaction that involves the removal of hydrogen, usually from an organic molecule. It is the reverse of hydrogenation. Dehydrogenation is important, both as a useful reaction and a serious problem. At its simplest, it is useful way of converting alkanes, which are relatively inert and thus low-valued, to olefins, which are reactive and thus more valuable. Alkenes are precursors to aldehydes, alcohols, polymers, and aromatics. As a problematic reaction, the fouling and inactivation of many catalysts arises via coking, which is the dehydrogenative polymerization of organic substrates.

A post-metallocene catalyst is a kind of catalyst for the polymerization of olefins, i.e., the industrial production of some of the most common plastics. "Post-metallocene" refers to a class of homogeneous catalysts that are not metallocenes. This area has attracted much attention because the market for polyethylene, polypropylene, and related copolymers is large. There is a corresponding intense market for new processes as indicated by the fact that, in the US alone, 50,000 patents were issued between 1991-2007 on polyethylene and polypropylene.

In chemistry, homogeneous catalysis is catalysis by a soluble catalyst in a solution. Homogeneous catalysis refers to reactions where the catalyst is in the same phase as the reactants, principally in solution. In contrast, heterogeneous catalysis describes processes where the catalysts and substrate are in distinct phases, typically solid-gas, respectively. The term is used almost exclusively to describe solutions and implies catalysis by organometallic compounds. Homogeneous catalysis is an established technology that continues to evolve. An illustrative major application is the production of acetic acid. Enzymes are examples of homogeneous catalysts.

<span class="mw-page-title-main">Transition metal pincer complex</span>

In chemistry, a transition metal pincer complex is a type of coordination complex with a pincer ligand. Pincer ligands are chelating agents that binds tightly through three adjacent coplanar sites in a meridional configuration. The inflexibility of the pincer-metal interaction confers high thermal stability to the resulting complexes. This stability is in part ascribed to the constrained geometry of the pincer, which inhibits cyclometallation of the organic substituents on the donor sites at each end. In the absence of this effect, cyclometallation is often a significant deactivation process for complexes, in particular limiting their ability to effect C-H bond activation. The organic substituents also define a hydrophobic pocket around the reactive coordination site. Stoichiometric and catalytic applications of pincer complexes have been studied at an accelerating pace since the mid-1970s. Most pincer ligands contain phosphines. Reactions of metal-pincer complexes are localized at three sites perpendicular to the plane of the pincer ligand, although in some cases one arm is hemi-labile and an additional coordination site is generated transiently. Early examples of pincer ligands were anionic with a carbanion as the central donor site and flanking phosphine donors; these compounds are referred to as PCP pincers.

<span class="mw-page-title-main">Olefin metathesis</span>

Olefin metathesis is an organic reaction that entails the redistribution of fragments of alkenes (olefins) by the scission and regeneration of carbon-carbon double bonds. Because of the relative simplicity of olefin metathesis, it often creates fewer undesired by-products and hazardous wastes than alternative organic reactions. For their elucidation of the reaction mechanism and their discovery of a variety of highly active catalysts, Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock were collectively awarded the 2005 Nobel Prize in Chemistry.

<span class="mw-page-title-main">Alkyne metathesis</span>

Alkyne metathesis is an organic reaction that entails the redistribution of alkyne chemical bonds. The reaction requires metal catalysts. Mechanistic studies show that the conversion proceeds via the intermediacy of metal alkylidyne complexes. The reaction is related to olefin metathesis.

Alkane metathesis is a class of chemical reaction in which an alkane is rearranged to give a longer or shorter alkane product. It is similar to olefin metathesis, except that olefin metathesis cleaves and recreates a carbon-carbon double bond, but alkane metathesis operates on a carbon-carbon single bond.

Coordination polymerisation is a form of polymerization that is catalyzed by transition metal salts and complexes.

<span class="mw-page-title-main">Robert H. Grubbs</span> American chemist and Nobel Laureate (1942–2021)

Robert Howard GrubbsForMemRS was an American chemist and the Victor and Elizabeth Atkins Professor of Chemistry at the California Institute of Technology in Pasadena, California. He was a co-recipient of the 2005 Nobel Prize in Chemistry for his work on olefin metathesis.

Ring-closing metathesis (RCM) is a widely used variation of olefin metathesis in organic chemistry for the synthesis of various unsaturated rings via the intramolecular metathesis of two terminal alkenes, which forms the cycloalkene as the E- or Z- isomers and volatile ethylene.

<span class="mw-page-title-main">Jean-Marie Basset</span> French chemist

Jean-Marie Basset is a French chemist, and is currently the director of KAUST catalysis research center.

In organometallic chemistry, a migratory insertion is a type of reaction wherein two ligands on a metal complex combine. It is a subset of reactions that very closely resembles the insertion reactions, and both are differentiated by the mechanism that leads to the resulting stereochemistry of the products. However, often the two are used interchangeably because the mechanism is sometimes unknown. Therefore, migratory insertion reactions or insertion reactions, for short, are defined not by the mechanism but by the overall regiochemistry wherein one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:

<span class="mw-page-title-main">Concurrent tandem catalysis</span>

Concurrent tandem catalysis (CTC) is a technique in chemistry where multiple catalysts produce a product otherwise not accessible by a single catalyst. It is usually practiced as homogeneous catalysis. Scheme 1 illustrates this process. Molecule A enters this catalytic system to produce the comonomer, B, which along with A enters the next catalytic process to produce the final product, P. This one-pot approach can decrease product loss from isolation or purification of intermediates. Reactions with relatively unstable products can be generated as intermediates because they are only transient species and are immediately used in a consecutive reaction.

In polymer chemistry, chain walking (CW) or chain running or chain migration is a mechanism that operates during some alkene polymerization reactions. CW can be also considered as a specific case of intermolecular chain transfer. This reaction gives rise to branched and hyperbranched/dendritic hydrocarbon polymers. This process is also characterized by accurate control of polymer architecture and topology. The extent of CW, displayed in the number of branches formed and positions of branches on the polymers are controlled by the choice of a catalyst. The potential applications of polymers formed by this reaction are diverse, from drug delivery to phase transfer agents, nanomaterials, and catalysis.

<span class="mw-page-title-main">Brookhart's acid</span> Chemical compound

Brookhart's acid is the salt of the diethyl ether oxonium ion and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr′4). It is a colorless solid, used as a strong acid. The compound was first reported by Volpe, Grant, and Brookhart in 1992.

<span class="mw-page-title-main">Vinyl iodide functional group</span>

In organic chemistry, a vinyl iodide functional group is an alkene with one or more iodide substituents. Vinyl iodides are versatile molecules that serve as important building blocks and precursors in organic synthesis. They are commonly used in carbon-carbon forming reactions in transition-metal catalyzed cross-coupling reactions, such as Stille reaction, Heck reaction, Sonogashira coupling, and Suzuki coupling. Synthesis of well-defined geometry or complexity vinyl iodide is important in stereoselective synthesis of natural products and drugs.

Karen Ila Goldberg is an American chemist, currently the Vagelos Professor of Energy Research at University of Pennsylvania. Goldberg is most known for her work in inorganic and organometallic chemistry. Her most recent research focuses on catalysis, particularly on developing catalysts for oxidation, as well as the synthesis and activation of molecular oxygen. In 2018, Goldberg was elected to the National Academy of Sciences.

Janis Louie is a Chemistry professor and Henry Eyring Fellow at The University of Utah. Louie contributes to the chemistry world with her research in inorganic, organic, and polymer chemistry.

References

  1. American Men and Women of Science, Thomson Gale 2004
  2. Brookhart, Maurice; Ogliaruso, Michael A.; Winstein, Saul. The homoaromatic 1-hydroxyhomotropylium cation. Journal of the American Chemical Society (1967), 89(8), 1965–6.
  3. Brookhart, Maurice; Lustgarten, Ronald K.; Winstein, Saul. Bridge flipping and rearrangement of norbornadienyl and 7-methylnorbornadienyl cations. Journal of the American Chemical Society (1967), 89(24), 6352–4.
  4. Lustgarten, Ronald K.; Brookhart, M.; Winstein, Saul. Direct observation of methyl-substituted 7-norbornadienyl and bicyclo[3.2.0]heptadienyl cations. Journal of the American Chemical Society (1968), 90(26), 7364–6.
  5. Richey, Herman G., Jr.; Nichols, James D.; Gassman, Paul G.; Fentiman, Allison F., Jr.; Winstein, S.; Brookhart, M.; Lustgarten, Ronald K. Classical 7-norbornenyl cation. Competition between aryl and alkenyl functions in stabilizing 7-aryl-7-norbornenyl cations. Journal of the American Chemical Society (1970), 92(12), 3783–4.
  6. Ittel, Steven D.; Johnson, Lynda K.; Brookhart, Maurice. Late-Metal Catalysts for Ethylene Homo- and Copolymerization. Chemical Reviews (Washington, D. C.) (2000), 100(4), 1169–1203.
  7. Janeta, Mateusz; Heidlas, Julius X.; Daugulis, Olafs; Brookhart, Maurice (2021). "2,4,6-Triphenylpyridinium: A Bulky, Highly Electron-Withdrawing Substituent That Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts". Angewandte Chemie International Edition. 60 (9): 4566–4569. doi:10.1002/anie.202013854. ISSN   1521-3773. OSTI   1755772. PMID   33230900. S2CID   227159941.
  8. Tran, Quan H.; Brookhart, Maurice; Daugulis, Olafs (2020-04-15). "New Neutral Nickel and Palladium Sandwich Catalysts: Synthesis of Ultra-High Molecular Weight Polyethylene (UHMWPE) via Highly Controlled Polymerization and Mechanistic Studies of Chain Propagation". Journal of the American Chemical Society. 142 (15): 7198–7206. doi:10.1021/jacs.0c02045. ISSN   0002-7863. PMID   32233435. S2CID   214770016.
  9. Brookhart, Maurice; Green, Malcolm L. H.; Parkin, Gerard. Agostic interactions in transition metal compounds. Proceedings of the National Academy of Sciences of the United States of America (2007), 104(17), 6908–6914.
  10. Lenges, Christian P.; White, Peter S.; Brookhart, Maurice. Hydrogenations Catalyzed by [C5Me5Rh(olefin)2] Complexes: Conversion of Alkoxysilanes to Silyl Enolates. Journal of the American Chemical Society (1999), 121(18), 4385–4396.
  11. Bailey, Brad C.; Schrock, Richard R.; Kundu, Sabuj; Goldman, Alan S.; Huang, Zheng; Brookhart, Maurice. Evaluation of Molybdenum and Tungsten Metathesis Catalysts for Homogeneous Tandem Alkane Metathesis. Organometallics (2009), 28(1), 355–360.
  12. Goldman, Alan S.; Roy, Amy H.; Huang, Zheng; Ahuja, Ritu; Schinski, William; Brookhart, Maurice. Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation-Olefin Metathesis. Science (Washington, DC, United States)(2006), 312(5771), 257–261.