The Nobel Prize in Chemistry 2005
Yves Chauvin, Robert H. Grubbs, Richard R. Schrock
Robert H. Grubbs
Born: 27 February 1942, Possum Trot, KY, USA
Affiliation at the time of the award: California Institute of Technology (Caltech), Pasadena, CA, USA
Prize motivation: "for the development of the metathesis method in organic synthesis"
Field: Organic chemistry
I was born at home in rural Kentucky in 1942, in a house that my father, Howard, had built. He did most of the construction himself and built it on land that his father had given him when he married my mother Faye. In some places, my birthplace is listed as Calvert City and in others Possum Trot. I was actually born between the two, so either one really is correct. Both of my parents were from small farm families in western Kentucky where most people stayed close to their homes. My many aunts, uncles and cousins formed a very supportive environment during my childhood. Although my grandmother spent her years working on the farm, she was very well educated and set a high standard that has resulted in many of her grandchildren becoming teachers and educators. She always read, told us stories and maintained an intellectual level that was unusual in rural Kentucky at that time. My mother was one of six surviving children of my grandmother and grandfather, a strawberry farmer. Because she was often sick when she was young and of little help on the farm, she was sent to college, where she received her teaching certificate after two years. She subsequently taught school for over 35 years as she moved from a one room school house teaching all grades, to a two room school teaching lower grades and finally to an elementary school where she taught first grade. Some of my early memories are of going to school with her when the baby sitter was not available and going to night and weekend classes with her while she finished her BA degree. It took her 28 years, but she finished her degree. She and my grandmother provided great role models for the value of education. Although my father did not attend college, he was a very gifted mechanic and a practical engineer. I grew up helping him to rebuild car engines, to install plumbing, to build houses and to work on my uncles' farms. After my father returned from serving two years in the US army in Europe during WW II, we moved into Paducah where he took night classes to become a diesel mechanic. He then spent many years working for the Tennessee Valley Authority, (TVA), operating and maintaining heavy equipment that was used in the construction of the extensive series of dams in Kentucky and Tennessee. The academic model of my mother and grandmother and the very practical, mechanical training from my father turned out to be perfect training for organic chemical research. I was the middle child between two sisters. My older sister became a teacher and has been heavily involved in art and painting. My younger sister became the first female journeyman electrician in western Kentucky and has spent a number of years working for the TVA.
As a child I was always interested in building things. Instead of buying candy, I would purchase nails which I used to construct things out of scrap wood. My mother always claimed that my spending my money on nails instead of on candy was why I was so skinny as a kid. As I grew older, farms in Kentucky provided me with many jobs in hauling hay and in cutting tobacco. In addition to helping fund my college years, these jobs helped me to meet an array of very interesting and amazing men and women.
My interest in science started in Junior High School where an outstanding science teacher, Mrs. Baumgardner, introduced me to the joys of science. In the 50's there were many excellent scientists in Paducah, Kentucky, who had settled there to become teachers after working in what we called the "Atomic Plant". This was a major uranium refining facility that was located in western Kentucky to take advantage of the power and production facilities resulting from the TVA construction in the area.
Since I had grown up with parents who had started life on farms in rural Kentucky and I had spent many hours working on farms, it was natural that I started college at the University of Florida as an Agricultural Chemistry major. This field combined my interests in science and agriculture. One of my summer jobs in college was in an animal nutrition laboratory where I analyzed steer feces all summer long. Fortunately, one of my friends was working in an organic laboratory for the summer and invited me to help him at night. He was working for Merle Battiste, a new faculty member at the University of Florida. I found that organic chemicals smelled much better than steer feces and that there was great joy in making new molecules. Battiste started me on the chemical journey and saved me from a life of analyzing animal matter. Shortly after joining his group, I read an organic text, Mechanisms and Structure in Organic Chemistry by E.S. Gould on reaction mechanisms which explained how chemical reactions take place. I was fascinated by being able to do rather simple chemical transformations to learn about the details of how organic compounds reacted at the molecular level. This direct coupling of simple observations with fundamental chemical reactions is the power of organic chemistry. Also, building new molecules was even more fun than building houses. The reactions of cyclopropenes served as the basis for most of my work in the Battiste group, and many years later a similar reaction of cyclopropenes opened the way to the synthesis of our first generation of catalysts. Battiste not only introduced me to organic research, but after he had trained me to be a productive researcher, he told me that I would have to leave his group. Although it would have been best for him for me to stay in his laboratory to finish my degree, he encouraged me to move on to a different group in a different part of the US to receive broader training. He encouraged me to go to Columbia University in New York City where I worked for Ron Breslow. Battiste had been Breslow's first PhD student. Just before going to Columbia, I heard a young Australian chemist, Rolli Pettit, who worked at the University of Texas, lecture at Florida. He talked about the stabilization of unstable molecules by coordination to transition metals. Rolli, who unfortunately died much too young, was an inspirational scientist who helped to direct me toward the use of metals in organic chemistry. For my graduate work, I initially chose a project related to the Pettit work and finished studying the anti-aromaticity of cyclobutadiene. It was an exciting time in the Breslow group. A number of students and postdoctoral fellows who have since gone on to stellar academic careers worked in the group at that time and, along with Breslow, provided an amazingly stimulating environment. Working on projects involving metals confirmed my desire to turn my research toward transition metal organometallic chemistry and I obtained an NIH fellowship to work with Jim Collman who had just moved to Stanford. At that time organometallic chemistry was in its infancy and it provided a fertile field for a mechanistic chemist. There appeared to be an incredible array of important catalytic processes emerging in the field while little was known about the fundamental transformation involved. Collman had developed a systematic method of discussing reaction types that provided a basis for starting to understand the steps in Catalytic processes. One of the most exciting of these processes was olefin metathesis. It turned out that completely new fundamental steps were required to understand this reaction.
In 1969, as I finished my fellowship with Collman, Michigan State University, (MSU), was the only school that offered me a position in which to start my independent academic career. Harold Hart, Mike Karabatsos, Gene LeGoff, Don Farnum, Bill Reusch and Pete Wagner served as my early mentors at MSU and provided a very supportive environment for a starting faculty member. After nine very productive years at MSU where I started my work in olefin metathesis and a number of other areas of catalysis, I was offered a position at Caltech in 1978. Numerous outstanding graduate students contributed to my program at MSU. One postdoctoral fellow, however, played a major role in developing my research program. Dr. Akira Miyashita, who died in 2004, brought a number of new techniques to the group as well as an exemplary work ethic. He moved with me to Caltech in 1978 where he helped to reestablish the group in California.
The faculty at Caltech had created a rich environment for the training of outstanding graduate students, and these students, along with creative postdoctoral fellows and new faculty colleagues allowed my program to grow in many directions to take advantage of the growing field of organometallic catalysts. Bob Ireland and Dave Evans helped me to return to organic synthesis and to the development of new synthetic processes based on transition metals, and Peter Dervan and Dennis Dougherty, who provided guidance in physical organic chemistry as well as friendship over many years. John Bercaw and Harry Gray kept me honest in inorganic chemistry. Shortly after I arrived at Caltech, Fred Tebbe, a DuPont chemist, reported the structure and reactions of the complex that we later named the "Tebbe Reagent." Working with Dave Evans and Stan Pine on sabbatical from CSULA, we demonstrated that this reagent provided the first general route for the conversion of esters to vinyl ethers. This work also provided the basis for our mechanistic work that resulted in the synthesis of the first metathesis active metallacyclobutane. Many of the lessons learned with the Tebbe reagent were important in later developments. We discovered that it was important to develop a commercial source of this organometallic reagent so that other researchers could try the reaction without making a major investment of time in developing the techniques for making the reagent. The utility of the reagent was always limited by its instability under normal laboratory conditions. It required special air and water free conditions for its use. The desire for ease of use drove the early development of the ruthenium catalysts. We pursued the ruthenium based catalysts since they did not suffer many of the instability problems that had limited the use of the earlier tungsten and molybdenum based catalysts. We also developed early commercial sources and later commercially viable methods for the production of the well defined ruthenium based catalysts. In my lecture I discussed many of the developments from this point that let to the discovery of the family of ruthenium based metathesis catalysts and I named key members of the group who contributed directly to their development. Surrounding the group who made the key discoveries were others who made equally significant contributions that served as the basis for the specifically listed advances.
The olefin metathesis mechanism was one of my first projects at MSU and my group explored various aspects of this reaction throughout my career. In addition, we explored other mechanistic questions. An early project returned me to my interest in cyclobutadiene and we designed a mechanistic study to determine if cyclobutadiene was really formed from the decomposition of the Pettit iron tricarbonyl complexes. Other studies explored the mechanism of the Ziegler catalysts in the polymerization of ethylene and propylene. Using isotopes and stereochemistry, while working along with Mike Steigerwald, we developed a method that determined the critical steps in this reaction. Other work involved the study of metallacyclopentanes, a class of complexes we had become interested in from our early mechanistic studies of metathesis. Although metallacyclopentanes are not important in olefin metathesis, they have been found to be important in a variety of other olefin dimerization reactions. In a similar way, the discoveries in olefin metathesis have led to new processes that can benefit from detailed mechanistic explorations. Many of our advances in ruthenium catalyst development were the result of applying the techniques developed earlier in our group in the study of other complex catalytic processes.
One of the important developments in the group was the growth of research in polymer chemistry. Many of the students and postdoctoral fellows who helped to develop our polymer program have moved on to outstanding careers and have helped to establish polymer chemistry in other universities. The polymer program has opened many new opportunities and has led the group in a number of directions from biomedical applications to the synthesis of new membranes and barrier films. Although ring opening olefin metathesis polymerization, (ROMP), provided the path into polymer science, the techniques learned have opened possibilities outside of olefin metathesis. For example, they have resulted in the development of a new material that has found applications in light adjustable interocular lenses.
In the present commercial environment, it is difficult for fundamental discoveries to be transitioned into large companies. After a number of early frustrations that resulted from attempts to move our work directly into major companies, we were involved in the creation of a company to aid in the transition of technology from discovery to product. Mike Giardello, in addition to developing the first commercially viable route to a ruthenium metathesis catalyst, has played a major role in establishing Materia, Inc., where many of the commercial applications of the ruthenium technology – and other metathesis based products – were developed.
It has been very pleasing that a process that we started to study from pure intellectual curiosity has resulted in new processes which have very practical applications. I hope the success of the process has been a sufficient reward for the patience of the granting agencies who have allowed me to follow the metathesis reaction on the wandering path that has resulted from many chance and unanticipated discoveries. There are still many turns left on the metathesis path.
During my career, over 200 students and postdoctoral fellows have worked in my research group. They have all left their mark. I thank them all for their hard work, for their creative contributions and for making chemistry fun.
During my second year at Columbia, I met a wonderful lady from Brooklyn, Helen O'Kane. She has been my companion and best friend since that time. I thank her and our three children, Barney, now a Professor of Chemistry at Dartmouth, Brendan, an MD resident at USC and Kathleen, a PhD in Clinical Psychology program at University of Hawaii, who have supported me professionally as well as personally during this chemical quest.
From Les Prix Nobel. The Nobel Prizes 2005, Editor Karl Grandin, [Nobel Foundation], Stockholm, 2006
This autobiography/biography was written at the time of the award and first published in the book series Les Prix Nobel. It was later edited and republished in Nobel Lectures. To cite this document, always state the source as shown above.Copyright © The Nobel Foundation 2005
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