Robert H. Grubbs

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Robert Grubbs
Robert Grubbs Royal Society.jpg
Robert Grubbs at the Royal Society admissions day in London, July 2018
Born
Robert Howard Grubbs

(1942-02-27) February 27, 1942 (age 77)
Nationality United States
Alma mater
Known forCatalysts for olefin metathesis in organic synthesis
Spouse(s)Helen O'Kane-Grubbs
Awards
Scientific career
Fields Organic chemistry
Institutions Stanford University
Michigan State University
California Institute of Technology
Thesis I. Cyclobutadiene Derivatives II. Studies of Cyclooctatetraene Iron Tricarbonyl Complexes  (1968)
Doctoral advisor Ronald Breslow [3]
Doctoral students SonBinh Nguyen
Website chche.divisions.caltech.edu/people/robert-h-grubbs

Robert Howard Grubbs ForMemRS (born February 27, 1942) is an American chemist and the Victor and Elizabeth Atkins Professor of Chemistry at the California Institute of Technology in Pasadena, California. [4] He was a co-recipient of the 2005 Nobel Prize in Chemistry for his work on olefin metathesis. [5] He is a co-founder of Materia, a University spin-off startup to produce catalysts. [6]

Contents

Early life and education

AIC Gold Medal recipient, 2010 Robert H. Grubbs HD2010 AIC Gold Medal 2.JPG
AIC Gold Medal recipient, 2010

Grubbs was born on February 27, 1942, on a farm in Marshall County, Kentucky, midway between Possum Trot and Calvert City. [7] [8] His parents were Howard and Faye Grubbs. [7] Faye Grubbs was a schoolteacher. After serving in World War II, the family moved to Paducah, Kentucky, where Howard Grubbs trained as a diesel mechanic, and Robert Grubbs attended Paducah Tilghman High School. [7] [8]

At the University of Florida, Robert Grubbs initially intended to study agriculture. However, he was convinced by professor Merle A. Battiste to switch to organic chemistry. [9] Working with Battiste, Grubbs became interested in how chemical reactions occur. [8] He received his B.S. in 1963 and M.S. in 1965 from the University of Florida. [9]

Next, Grubbs attended Columbia University, where he worked with Ronald Breslow [3] on the antiaromaticity of cyclobutadiene. This work aroused his interest in metals and organometallic compounds which contain carbon-metal bonds. Grubbs received his PhD in 1968. [3] [8]

Career and research

Grubbs worked with James Collman at Stanford University as a National Institutes of Health fellow during 1968–1969. With Collman, he began to systematically investigate catalytic processes in organometallic chemistry, a relatively new area of research. [8]

In 1969, Grubbs was then appointed to the faculty of Michigan State University, where he began his work on olefin metathesis. Harold Hart, Gerasimos J. Karabatsos, Gene LeGoff, Don Farnum, Bill Reusch and Pete Wagner served as his early mentors at MSU. [8] He was an assistant professor from 1969 to 1973, and an associate professor from 1973 to 1978. [10] He received a Sloan Fellowship for 1974–1976. [11] In 1975, he went to the Max Planck Institute for Coal Research in Mülheim, Germany on a fellowship from the Alexander von Humboldt Foundation. [12]

In 1978 Grubbs moved to California Institute of Technology as a professor of chemistry. As of 1990 he became the Victor and Elizabeth Atkins Professor of Chemistry. [13] [14]

Grubbs's main research interests are in organometallic chemistry and synthetic chemistry, particularly the development of novel catalysts for olefin metathesis. In olefin metathesis, a catalyst is used to break the bonds of carbon molecules, which can then re-form to create chemical bonds in new ways, producing new compounds with unique properties. [9] [15] The basic technique can be used for creation of polymers, pharmaceuticals and petrochemicals [16] and has broad applications in areas including pharmaceuticals, biotechnology, agriculture, and plastics. [9]

Grubbs has been instrumental in developing a family of ruthenium catalysts including Grubbs catalyst for olefin metathesis. [17] He has studied olefin transformations for ring-closing metathesis (RCM), [18] cross-metathesis reaction (CMR), [19] and ring-opening metathesis polymerization (ROMP) with cyclic olefins such as norbornene. [20] He has also contributed to the development of "living polymerization", in which the termination ability of a polymerization reaction is removed. The polymer will continue to replicate until a quenching agent is presented. [21]

The Grubbs group successfully polymerized the 7-oxo norbornene derivative using ruthenium trichloride, osmium trichloride as well as tungsten alkylidenes. [22] They identified a Ru(II) carbene as an effective metal center and in 1992 published the first well-defined, ruthenium-based olefin metathesis catalyst, (PPh3)2Cl2Ru=CHCH=CPh2: [20]

Metathesis Grubbs 1992 MetathesisGrubbs1992.svg
Metathesis Grubbs 1992

The corresponding tricyclohexylphosphine complex (PCy3)2Cl2Ru=CHCH=CPh2 was also shown to be active. [23] This work culminated in the now commercially available 1st generation Grubbs catalyst in 1995. [24] [25] [26] Second generation catalysts have been developed as well. [27] [28]

Ruthenium is stable in air and has higher selectivity and lower reactivity than molybdenum, the most promising of the previously discovered catalysts. In addition, Grubbs took a green chemistry approach to catalysis that reduced the potential to create hazardous waste. Grubbs catalyst has become a standard for general metathesis applications in ordinary laboratories. [4] [17] [27]

By controlling the catalyst used, it becomes possible to synthesize polymers with specialized structures and functional capabilities, including cyclic olefins, alternating copolymers, and multiblock copolymers. [15] Using catalysts allows chemists to speed up chemical transformations and to lower the cost of what were previously complicated multi-step industrial processes. [29]

Commercial activities

Both first and second generation Grubbs catalysts are commercially available from Materia, a startup company that Grubbs co-founded with Mike Giardello in Pasadena, California in 1998. [24] [29] [30] Materia has been able to obtain exclusive rights to manufacture many of the known olefin catalysts. [31] Under Giardello, Materia was able to sell their catalysts through Sigma-Aldrich 's chemicals catalogue. Sigma-Aldrich became their exclusive worldwide provider. [29] [32] In 2008, Materia partnered with Cargill to form Elevance Renewable Sciences to produce specialty chemicals from renewable oils, [33] including biofuels. [34]

Grubbs is a member of the Reliance Innovation Council formed by Reliance Industries Limited, India. [35]

Grubbs is a member of the USA Science and Engineering Festival's Advisory Board. [36]

Awards and honors

Grubbs received the 2005 Nobel Prize in Chemistry, along with Richard R. Schrock and Yves Chauvin, for his work in the field of olefin metathesis. [5] [37] He has received a number of other awards and honors as well, including the following:

Personal life

While at Columbia University, Grubbs also met his future wife, Helen O'Kane, with whom he has three children: Barney, (born 1972), Brendan H. (born 1974) and Kathleen (Katy) (born 1977). [8] [53]

Related Research Articles

Organometallic chemistry study of chemical compounds containing at least one bond between a carbon atom of an organic compound and a metal

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 alkaline, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and tin, 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 polymer chemistry, living polymerization is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of chain propagation. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar. Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different monomer. Additional advantages are predetermined molar mass and control over end-groups.

In polymer chemistry, ring-opening polymerization (ROP) is a form of chain-growth polymerization, in which the terminus of a polymer chain attacks cyclic monomers to form a longer polymer. The reactive center can be radical, anionic or cationic. Some cyclic monomers such as norbornene or cyclooctadiene can be polymerized to high molecular weight polymers by using metal catalysts. ROP is a versatile method for the synthesis of biopolymers.

Grubbs catalyst chemical compound

Grubbs catalysts are a series of transition metal carbene complexes used as catalysts for olefin metathesis. They are named after Robert H. Grubbs, the chemist who supervised their synthesis. Several generations of the catalyst have been developed. Grubbs catalysts tolerate many functional groups in the alkene substrates, are air-tolerant, and are compatible with a wide range of solvents. For these reasons, Grubbs catalysts have become popular in synthetic organic chemistry. Grubbs, together with Richard R. Schrock and Yves Chauvin, won the Nobel Prize in Chemistry in recognition of their contributions to the development of olefin metathesis.

Olefin metathesis redistribution of olefinic (alkene) bonds

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.

Norbornene unsaturated, bicyclic hydrogencarbon

Norbornene or norbornylene or norcamphene is a bridged cyclic hydrocarbon. It is a white solid with a pungent sour odor. The molecule consists of a cyclohexene ring with a methylene bridge between carbons 1 and 4. The molecule carries a double bond which induces significant ring strain and significant reactivity.

Richard R. Schrock American chemist

Richard Royce Schrock is an American chemist and Nobel laureate recognized for his contributions to the olefin metathesis reaction used in organic chemistry.

Yves Chauvin French chemist and Nobel Prize winner in Chemistry

Yves Chauvin was a French chemist and Nobel Prize laureate. He was honorary research director at the Institut français du pétrole and a member of the French Academy of Science. He was known for his work for deciphering the process of metathesis for which he was awarded the 2005 Nobel Prize in Chemistry along with Robert H. Grubbs and Richard R. Schrock.

Ring-closing metathesis, or 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.

Ring-opening metathesis polymerization (ROMP) is a type of olefin metathesis chain-growth polymerization. The driving force of the reaction is relief of ring strain in cyclic olefins. A variety of heterogeneous and homogeneous catalysts have been developed. Most large-scale commercial processes rely on the former while some fine chemical syntheses rely on the homogeneous catalysts. Catalysts are based on transition metals such as W, Mo, Re, Ru, and Ti.

Acyclic diene metathesis or 'ADMET' is a special type of olefin metathesis used to polymerize terminal dienes to polyenes:

Organoruthenium chemistry

Organoruthenium chemistry is the chemistry of organometallic compounds containing a carbon to ruthenium chemical bond. Several organoruthenium catalysts are of commercial interest and organoruthenium compounds have been considered for cancer therapy. The chemistry has some stoichiometric similarities with organoiron chemistry, as iron is directly above ruthenium in group 8 of the periodic table. The most important reagents for the introduction of ruthenium are ruthenium(III) chloride and triruthenium dodecacarbonyl.

Didier Astruc French chemist

Didier Astruc carried out his studies in chemistry in Rennes. After a Ph. D. with professor R. Dabard in organometallic chemistry, he did post-doctoral studies with professor R. R. Schrock at the Massachusetts Institute of Technology Cambridge, Massachusetts, in the U.S. and later a sabbatical year with professor K. P. C. Vollhardt at the University of California at Berkeley. He became a CNRS Director of research in Rennes, then in 1983 full Professor of Chemistry at the University Bordeaux 1. He is known for his work on “Electron-Reservoir” complexes and dendritic molecular batteries, catalytic processes using nanoreactors and molecular recognition using gold nanoparticles and metallodendrimers. He is the author of three books, scientific publications and the editor of five books or special issues. He has been a member of the National CNRS committee from 2000 to 2008 and the President of the Coordination Chemistry Division of the Société Française de Chimie from 2000 to 2004. Didier Astruc is on the Thompson-Reuters list of the top 100 chemists who have achieved the highest citation impact scores for their chemistry papers published between 2000 and 2010. and on the list of the Highest Cited Researchers 2015 and 2016 (Thomson-Reuters). and 2017(Clarivate Analytics)

Ethenolysis is a chemical process in which internal olefins are degraded using ethylene as the reagent. The reaction is an example of cross metathesis. The utility of the reaction is driven by the low cost of ethylene as a reagent and the selectivity with which it forms compounds containing a terminal alkene functional group (α-olefins). The general reaction equation is:

Frederick N. Tebbe American chemist

Frederick Nye Tebbe was a chemist known for his work on organometallic chemistry. Tebbe was born in Oakland, California on March 20, 1935. His father, Charles L. Tebbe, worked for the United States Forest Service so Fred’s early education took place in Montana, Oregon, Maryland and Pennsylvania. He married Margaret Manzer in 1960, and they had a son and a daughter. He died of pancreatic cancer at his home in Delaware on September 28, 1995.

Herbert S. Eleuterio

Herbert S. Eleuterio is an American industrial chemist noted for technical contributions to catalysis, polymerization, industrial research management, and science education. In particular, he discovered the olefin metathesis reaction and several novel fluoropolymers. Additionally, he explored techniques for research leadership, especially methods for fostering collaboration, globalization, and scientific creativity.

Functionalized polyolefins are olefin polymers with polar and nonpolar functionalities attached onto the polymer backbone. There has been an increased interest in functionalizing polyolefins due to their increased usage in everyday life. Polyolefins are virtually ubiquitous in everyday life, from consumer food packaging to biomedical applications; therefore, efforts must be made to study catalytic pathways towards the attachment of various functional groups onto polyolefins in order to affect the material's physical properties.

Zhan catalyst group of chemical compounds

A Zhan catalyst is a type of ruthenium-based organometallic complex used in olefin metathesis. This class of chemicals is named after the chemist who first synthesized them, Zheng-Yun J. Zhan.

Metallacyclopentanes

In organometallic chemistry, metallacyclopentanes are compounds with the formula LnM(CH2)4 (Ln = ligands, and M = metal). They are a type of metallacycle. Metallacyclopentanes are intermediates in some metal-catalysed reactions in homogeneous catalysis.

Carbonyl olefin metathesis is a type of metathesis reaction that entails, formally, the redistribution of fragments of an alkene and a carbonyl by the scission and regeneration of carbon-carbon and carbon-oxygen double bonds respectively. It is a powerful method in organic synthesis using simple carbonyls and olefins and converting them into less accessible products with higher structural complexity.

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