Anthony Joseph Arduengo III
Encyclopedia
Anthony Joseph Arduengo, III is the Saxon Professor of Chemistry
at the University of Alabama
and an adjunct professor at the Institute for Inorganic Chemistry of Braunschweig University of Technology in Germany. He is notable for his work on chemical compounds with unusual valency
, especially in the field of stable carbene research.
, Florida
. He grew up in the Atlanta, Georgia
area. His father was a pressman and mechanic with the Atlanta Journal-Constitution and instilled his son with an interest and skill for all things mechanical and scientific. By the age of 16, he and his father had built his first car from miscellaneous parts. The car was registered as street-legal and road-worthy. With some re-engineering, the car was later fitted to run on alternate fuels including alcohol and hydrogen (which would foretell Arduengo's professional research involvement with President Bush
's 2003 National Hydrogen Fuel Initiative (HFI) and United States Department of Energy
's Chemical Hydrogen Storage
Program by more than 30 years).
. In 1969 he left high school with enrollment in Georgia Tech's Joint Enrollment Program for High School Students (JEPHS). He obtained his BSc (1974, cum laude
) and his PhD (1976) at Georgia Tech
, advised by Edward M. Burgess. That made him an academic descendant of Justus von Liebig
. As an undergraduate at Georgia Tech
, Arduengo's research activities began in the laboratory of Professor Charles L. Liotta. He was awarded NSF
undergraduate fellowships in 1972 & 1973 when he had moved to research in the Burgess group.
As an undergraduate, Arduengo was a member of the Georgia Tech Band and served as Executive Officer and Captain for that organization. In 1971 he was inducted into the Iota chapter of ΚΚΨ
. In 1972 he was tapped by the Alpha Eta Circle of ΟΔΚ
; later serving as Secretary and President for the local Circle.
from 1976 to 1977 and from 1984 to 1998, and assistant professor at the University of Illinois from 1977 to 1984. He is currently the Saxon Chair of Chemistry at the University of Alabama
and holds a position as adjunct professor at the Technische Universität in Braunschweig
, Germany
.
In DuPont's Central Research and Development Department
, Arduengo began his career in the Chemical Sciences Section (1977 & on return in 1984). In 1988 he was appointed Research Leader. A move into the Polymer Science section of CR&D
in 1991 was accompanied by promotion to Group Leader. His final position with DuPont
was as Research Fellow which he attained in 1995. The award of an Alexander von Humboldt Senior Research Prize
in 1996 began Arduengo's transition back into academe. The one year Humboldt award was spent in Braunschweig
, Germany
at the Technical University. On return to DuPont
, Arduengo maintained a guest Professor appointment in Braunschweig
, and in 1999 also made the transition to academe in the U.S. with his assumption of the Saxon Chair in Chemistry at The University of Alabama
in Tuscaloosa
.
. As a graduate student in the Burgess group, his research involved organo-main group element
chemistry, specifically, thiocarbonyl ylides, and low-coordinate hypervalent sulfur
compounds.
, Arduengo became a member of the exploratory chemistry group of Howard Simmons
in CR&D
. His first research project involved trimethylsilyl
ester
s of inorganic acid
s as reagent
s for organic synthesis
.
chemistry, and molecules containing unusual valency
. His first publications involving the chemistry of electron-deficient carbene
s occurred during this period. This work with electron deficient carbenes led to the first structure determinations on a nitrile ylide
and a carbonyl ylide
. His later work with carbene
chemistry would become his most recognized contribution to the field of chemistry (vide infra). During the Illinois years Arduengo had a close collaboration with his colleague J.C. Martin
who was a physical-organic chemist also working on organo-main group element
chemistry and hypervalency. Many of the technical discussions between Martin and Arduengo would take place over lunch (the choice of restaurants often influenced by the quality of the napkins for writing chemical structures). To facilitate discussions about unusual molecular structures and bonding for main-group element
centers, Martin and Arduengo devised the N-X-L nomenclature system. The synthesis and characterization of the first compound with a planar T-shaped, 10-electron
3-coordinate bonding arrangement at a phosphorus
atom, ADPO, was also accomplished by the Arduengo group at Illinois and paved the way for a range of novel main-group element
chemistry (including the discovery of edge inversion) on his return to DuPont
. The final Illinois research extended the newly discovered ADPO chemistry to the arsenic analog (ADAsO).
in 1984, Arduengo resumed a position in CR&D
and continued the research into the recently discovered ADPO molecule and related structures. This line of research proved to be extremely fruitful and resulted in a steady string of publications on new and unusual bonding arrangements. The ADPO related chemistry provided a basis for the discovery of a new inverson process, edge inverson, which was fully characterized and modelled by the collaborative work of Arduengo and David A. Dixon at DuPont
. Additionally, the DuPont
team provided experimental verification on the new inversion pathway at 3-coordinate phosphorus
centers and a 4-coordinate germanium molecule.
Arduengo's work with DuPont
also involved a number of applied projects including the flexible polyimide
film, Kapton
®-ZT, that is widely used in electronics for flexible printed circuits, connections, and insulation. Arduengo's research at DuPont
often coalesced with his other hobbies outside the laboratory; for example with sports cars (cf. photo in the summary box above). He contributed to development of low VOC
automotive coatings by devising catalysts for a novel cross-link
ing chemistry used by DuPont
Performance Coatings in next-generation low-VOC
paints. Eventually, DuPont
waterborne performance coatings would be used by Lotus
on their Elise
and Exige
models. Arduengo's effort on the industrial-scale syntheses of the catalysts for the paints on which he worked would launch his re-entry into the area of carbene
chemistry, but this time it was to be nucleophilic
rather than electrophilic
carbenes. The observation that the catalyst syntheses were well tolerant of varied reaction conditions and substituents led Arduengo to postulate that the imidazol-2-ylidenes that were intermediates
in the syntheses had to be far more stable than the then conventional wisdom would allow.
As Arduengo's involvement in the automotive coatings program came to an end, he submitted a proposal to the management in CR&D
to isolated these apparently stable carbenes and study their chemistry. The proposal was soundly declined with the admonition that he should have certainly known better than to make such a suggestion in light of the long history of carbene
chemistry that firmly established them as reactive intermediate
s that could not be isolated as stable entities. However, Arduengo (already well-aware of the history) had the starting materials on hand for the chemistry and decided to proceed with the experiments. “Arduengo’s gamble paid off. In 1991, more than 150 years after the first attempt ...” a stable crystalline carbene was isolated and characterized in laboratories at DuPont
. After the first successful reaction to produce a stable carbene
, Arduengo won the support of DuPont
management and research in this area continued. Carbenes bearing a variety of substituent groups were prepared and characterized. The saturated imidazolin-2-ylidenes
that were extensively investigated by Hans-Werner Wanzlick
thirty years earlier (without isolation) were now also shown to be stable enough to isolate with appropriate substituents at nitrogen. An air-stable carbene was produced. The chemistry was extended to include thiazol-2-ylidenes (conjectured to exist in 1957 as a reactive intermediate
in the vitamin B1 catalytic cycle
, but not isolated for 40 years). The imidazol-2-ylidenes were extensively characterized by their NMR
properties, photo-electron spectroscopy
, and exact experimental electron density mapping by X-ray
and neutron diffraction
techniques.
The Arduengo group's characterization of stable carbene
s was complemented by a wide ranging exploration of their chemistry. This new chemistry included carbene
reactions with numerous element centers including iodine
, aluminum, copper
, silver
, magnesium
, zinc
, germanium
, nickel
, platinum
, lanthanide
s, and hydrogen
in the form a bis(carbene)-proton complex. Arduengo's research from 1996 also reflects his interaction with his host for his Alexander von Humboldt Research Prize
, Professor Reinhard Schmutzler. His carbene
chemistry conducted from Braunschweig included reactivity studies of imidazol-2-ylidenes with fluorinated inorganic compounds. New structures included carbene•phenyltetrafluorophosphorane, carbene•PF5, carbene•AsF5, carbene•SbF5, and carbene•BF3 adducts. Arduengo's final work on carbene
s at DuPont
included synthesis and characterization of carbene·alkaline earth metal
, carbene•antimony
, carbene•cadmium
, and carbene•lithium
adducts. Reactions of carbene
s with phosphinidene
s were also reported from Arduengo's laboratory in addition to insertion reactions of imidazolin-2-ylidenes
.
In 1998, Arduengo and coworkers carefully re-examined the earlier attempts to produce stable carbenes in Wanzlick's laboratory in light of the knowledge and experience gained from the recent successful experiments at DuPont. Although the majority of Wanzlick's work on the saturated imidazolin-2-ylidenes
would have been expected to yield dimers in the absence of bulky substituents on nitrogen, a single (unsaturated) imidazol-2-ylidene, 1,3,4,5-tetraphenylimidazol-2-ylidene, remained as an example of a carbene that could (should) have been isolable. The re-examination of Wanzlick's original procedure identified some key experimental features that would have hindered the original researchers. With these problems corrected, the DuPont scientists were able to isolate the target carbene and fully characterize it including an X-ray structure determination. In a tribute to Hans-Werner Wanzlick, these results were published under the title “1,3,4,5-Tetraphenylimidazol-2-ylidene: The Realization of Wanzlick's Dream.”
fused imidazol-2-ylidene. Research into the unusual valency in diphosphacyclobutane-2,4-diyls has been reported from the Arduengo group in collaboration with Professors Masaaki Yoshifuji and Shigekazu Ito. Arduengo also directs research programs into Chemical Hydrogen Storage and nonlinear optical material
s.
Chemistry
Chemistry is the science of matter, especially its chemical reactions, but also its composition, structure and properties. Chemistry is concerned with atoms and their interactions with other atoms, and particularly with the properties of chemical bonds....
at the University of Alabama
University of Alabama
The University of Alabama is a public coeducational university located in Tuscaloosa, Alabama, United States....
and an adjunct professor at the Institute for Inorganic Chemistry of Braunschweig University of Technology in Germany. He is notable for his work on chemical compounds with unusual valency
Valence (chemistry)
In chemistry, valence, also known as valency or valence number, is a measure of the number of bonds formed by an atom of a given element. "Valence" can be defined as the number of valence bonds...
, especially in the field of stable carbene research.
Early life
Anthony "Bo" Arduengo was born in 1952 in TampaTâmpa
Tâmpa may refer to several villages in Romania:* Tâmpa, a village in Băcia Commune, Hunedoara County* Tâmpa, a village in Miercurea Nirajului, Mureş County* Tâmpa, a mountain in Braşov city...
, Florida
Florida
Florida is a state in the southeastern United States, located on the nation's Atlantic and Gulf coasts. It is bordered to the west by the Gulf of Mexico, to the north by Alabama and Georgia and to the east by the Atlantic Ocean. With a population of 18,801,310 as measured by the 2010 census, it...
. He grew up in the Atlanta, Georgia
Georgia (U.S. state)
Georgia is a state located in the southeastern United States. It was established in 1732, the last of the original Thirteen Colonies. The state is named after King George II of Great Britain. Georgia was the fourth state to ratify the United States Constitution, on January 2, 1788...
area. His father was a pressman and mechanic with the Atlanta Journal-Constitution and instilled his son with an interest and skill for all things mechanical and scientific. By the age of 16, he and his father had built his first car from miscellaneous parts. The car was registered as street-legal and road-worthy. With some re-engineering, the car was later fitted to run on alternate fuels including alcohol and hydrogen (which would foretell Arduengo's professional research involvement with President Bush
George W. Bush
George Walker Bush is an American politician who served as the 43rd President of the United States, from 2001 to 2009. Before that, he was the 46th Governor of Texas, having served from 1995 to 2000....
's 2003 National Hydrogen Fuel Initiative (HFI) and United States Department of Energy
United States Department of Energy
The United States Department of Energy is a Cabinet-level department of the United States government concerned with the United States' policies regarding energy and safety in handling nuclear material...
's Chemical Hydrogen Storage
Hydrogen storage
Hydrogen storage describes the methods for storing H2 for subsequent use. The methods span many approaches, including high pressures, cryogenics, and chemical compounds that reversibly release H2 upon heating...
Program by more than 30 years).
Education
Arduengo attended Bouldercrest and Meadowview Elementary Schools, and Walker High SchoolWalker High School (Atlanta, Georgia)
Walker High School was a DeKalb County, Georgia high school, on 1804 Bouldercrest Road SE. Atlanta, GA 30316 Southeast of Atlanta, Georgia. It was built in 1964 - and named after Southern Civil War General John George Walker born in - Jefferson City, Missouri...
. In 1969 he left high school with enrollment in Georgia Tech's Joint Enrollment Program for High School Students (JEPHS). He obtained his BSc (1974, cum laude
Latin honors
Latin honors are Latin phrases used to indicate the level of academic distinction with which an academic degree was earned. This system is primarily used in the United States, Canada, and in many countries of continental Europe, though some institutions also use the English translation of these...
) and his PhD (1976) at Georgia Tech
Georgia Institute of Technology
The Georgia Institute of Technology is a public research university in Atlanta, Georgia, in the United States...
, advised by Edward M. Burgess. That made him an academic descendant of Justus von Liebig
Justus von Liebig
Justus von Liebig was a German chemist who made major contributions to agricultural and biological chemistry, and worked on the organization of organic chemistry. As a professor, he devised the modern laboratory-oriented teaching method, and for such innovations, he is regarded as one of the...
. As an undergraduate at Georgia Tech
Georgia Institute of Technology
The Georgia Institute of Technology is a public research university in Atlanta, Georgia, in the United States...
, Arduengo's research activities began in the laboratory of Professor Charles L. Liotta. He was awarded NSF
National Science Foundation
The National Science Foundation is a United States government agency that supports fundamental research and education in all the non-medical fields of science and engineering. Its medical counterpart is the National Institutes of Health...
undergraduate fellowships in 1972 & 1973 when he had moved to research in the Burgess group.
As an undergraduate, Arduengo was a member of the Georgia Tech Band and served as Executive Officer and Captain for that organization. In 1971 he was inducted into the Iota chapter of ΚΚΨ
Kappa Kappa Psi
Kappa Kappa Psi is a fraternity for college and university band members. It was founded on November 27, 1919 at Oklahoma Agricultural and Mechanical College in Stillwater, Oklahoma. William Scroggs, now regarded as the "Founder," together with "Mr. Kappa Kappa Psi" A...
. In 1972 he was tapped by the Alpha Eta Circle of ΟΔΚ
Omicron Delta Kappa
Omicron Delta Kappa, or ΟΔΚ, also known as The Circle, or more commonly ODK, is a national leadership honor society. It was founded December 3, 1914, at Washington & Lee University in Lexington, Virginia, by 15 student and faculty leaders. Chapters, known as Circles, are located on over 300...
; later serving as Secretary and President for the local Circle.
Career
Arduengo was a research scientist at DuPontDuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
from 1976 to 1977 and from 1984 to 1998, and assistant professor at the University of Illinois from 1977 to 1984. He is currently the Saxon Chair of Chemistry at the University of Alabama
University of Alabama
The University of Alabama is a public coeducational university located in Tuscaloosa, Alabama, United States....
and holds a position as adjunct professor at the Technische Universität in Braunschweig
Braunschweig
Braunschweig , is a city of 247,400 people, located in the federal-state of Lower Saxony, Germany. It is located north of the Harz mountains at the farthest navigable point of the Oker river, which connects to the North Sea via the rivers Aller and Weser....
, Germany
Germany
Germany , officially the Federal Republic of Germany , is a federal parliamentary republic in Europe. The country consists of 16 states while the capital and largest city is Berlin. Germany covers an area of 357,021 km2 and has a largely temperate seasonal climate...
.
In DuPont's Central Research and Development Department
DuPont Central Research
In 1957, the research organization of the Chemicals Department of E. I. du Pont de Nemours and Company was renamed Central Research Department, beginning the history of the premier scientific organization within DuPont and one of the foremost industrial laboratories devoted to basic science...
, Arduengo began his career in the Chemical Sciences Section (1977 & on return in 1984). In 1988 he was appointed Research Leader. A move into the Polymer Science section of CR&D
DuPont Central Research
In 1957, the research organization of the Chemicals Department of E. I. du Pont de Nemours and Company was renamed Central Research Department, beginning the history of the premier scientific organization within DuPont and one of the foremost industrial laboratories devoted to basic science...
in 1991 was accompanied by promotion to Group Leader. His final position with DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
was as Research Fellow which he attained in 1995. The award of an Alexander von Humboldt Senior Research Prize
Humboldt Prize
The Humboldt Prize, also known as the Humboldt Research Award, is an award given by the Alexander von Humboldt Foundation to internationally renowned scientists and scholars, and is currently valued at € 60,000 with the possibility of further support during the prize winner's life. Up to one...
in 1996 began Arduengo's transition back into academe. The one year Humboldt award was spent in Braunschweig
Braunschweig
Braunschweig , is a city of 247,400 people, located in the federal-state of Lower Saxony, Germany. It is located north of the Harz mountains at the farthest navigable point of the Oker river, which connects to the North Sea via the rivers Aller and Weser....
, Germany
Germany
Germany , officially the Federal Republic of Germany , is a federal parliamentary republic in Europe. The country consists of 16 states while the capital and largest city is Berlin. Germany covers an area of 357,021 km2 and has a largely temperate seasonal climate...
at the Technical University. On return to DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
, Arduengo maintained a guest Professor appointment in Braunschweig
Braunschweig
Braunschweig , is a city of 247,400 people, located in the federal-state of Lower Saxony, Germany. It is located north of the Harz mountains at the farthest navigable point of the Oker river, which connects to the North Sea via the rivers Aller and Weser....
, and in 1999 also made the transition to academe in the U.S. with his assumption of the Saxon Chair in Chemistry at The University of Alabama
University of Alabama
The University of Alabama is a public coeducational university located in Tuscaloosa, Alabama, United States....
in Tuscaloosa
Tuscaloosa
Tuscaloosa is the name of two places in the United States of America:*Tuscaloosa, Alabama*Tuscaloosa County, AlabamaThere is also:*USS Tuscaloosa , U.S. Navy New Orleans-class heavy cruiser*USS Tuscaloosa , U.S...
.
Graduate Research at Georgia Tech
Arduengo's research interests focus largely on the chemistry of new or unusual bonding arrangements, and unusual valencyValence (chemistry)
In chemistry, valence, also known as valency or valence number, is a measure of the number of bonds formed by an atom of a given element. "Valence" can be defined as the number of valence bonds...
. As a graduate student in the Burgess group, his research involved organo-main group element
Main group element
In chemistry and atomic physics, main group elements are elements in groups whose lightest members are represented by helium, lithium,...
chemistry, specifically, thiocarbonyl ylides, and low-coordinate hypervalent sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...
compounds.
DuPont 1977
In 1977 when he joined DuPontDuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
, Arduengo became a member of the exploratory chemistry group of Howard Simmons
Howard Ensign Simmons, Jr.
Howard Ensign Simmons, Jr. was an American chemist who discovered the Simmons-Smith reaction.In 1976, Dr. Simmons served as Chair of the Organic division of the American Chemical Society.-References:...
in CR&D
DuPont Central Research
In 1957, the research organization of the Chemicals Department of E. I. du Pont de Nemours and Company was renamed Central Research Department, beginning the history of the premier scientific organization within DuPont and one of the foremost industrial laboratories devoted to basic science...
. His first research project involved trimethylsilyl
Trimethylsilyl
A trimethylsilyl group is a functional group in organic chemistry. This group consists of three methyl groups bonded to a silicon atom [−Si3], which is in turn bonded to the rest of a molecule...
ester
Ester
Esters are chemical compounds derived by reacting an oxoacid with a hydroxyl compound such as an alcohol or phenol. Esters are usually derived from an inorganic acid or organic acid in which at least one -OH group is replaced by an -O-alkyl group, and most commonly from carboxylic acids and...
s of inorganic acid
Mineral acid
A mineral acid is an acid derived from one or more inorganic compounds. A mineral acid is not organic and all mineral acids release hydrogen ions when dissolved in water.-Characteristics:...
s as reagent
Reagent
A reagent is a "substance or compound that is added to a system in order to bring about a chemical reaction, or added to see if a reaction occurs." Although the terms reactant and reagent are often used interchangeably, a reactant is less specifically a "substance that is consumed in the course of...
s for organic synthesis
Organic synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the construction of organic compounds via organic reactions. Organic molecules can often contain a higher level of complexity compared to purely inorganic compounds, so the synthesis of organic compounds has...
.
University of Illinois 1978-1984
At Illinois Arduengo examined more broadly the areas of organo-main group elementMain group element
In chemistry and atomic physics, main group elements are elements in groups whose lightest members are represented by helium, lithium,...
chemistry, and molecules containing unusual valency
Valence (chemistry)
In chemistry, valence, also known as valency or valence number, is a measure of the number of bonds formed by an atom of a given element. "Valence" can be defined as the number of valence bonds...
. His first publications involving the chemistry of electron-deficient carbene
Carbene
In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is RR'C:, but the carbon can instead be double-bonded to one group. The term "carbene" may also merely refer to the compound H2C:, also called...
s occurred during this period. This work with electron deficient carbenes led to the first structure determinations on a nitrile ylide
Nitrile ylide
Nitrile ylides also known as nitrilium ylides, or nitrilium methylides are generally reactive intermediates. Usually, they cannot be isolated. However, a structure has been determined on a by X-ray crystallography. As ylides, they possess a negative charge and a positive charge on adjacent atoms....
and a carbonyl ylide
Ylide
An ylide or ylid is a neutral dipolar molecule containing a formally negatively charged atom directly attached to a hetero atom with a formal positive charge , and in which both atoms have full octets of electrons. Ylides are thus 1,2-dipolar compounds...
. His later work with carbene
Carbene
In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is RR'C:, but the carbon can instead be double-bonded to one group. The term "carbene" may also merely refer to the compound H2C:, also called...
chemistry would become his most recognized contribution to the field of chemistry (vide infra). During the Illinois years Arduengo had a close collaboration with his colleague J.C. Martin
James Cullen Martin
James Cullen Martin was an American chemist. He specialized in organic chemistry and main group element chemistry with an emphasis on physical organic chemistry....
who was a physical-organic chemist also working on organo-main group element
Main group element
In chemistry and atomic physics, main group elements are elements in groups whose lightest members are represented by helium, lithium,...
chemistry and hypervalency. Many of the technical discussions between Martin and Arduengo would take place over lunch (the choice of restaurants often influenced by the quality of the napkins for writing chemical structures). To facilitate discussions about unusual molecular structures and bonding for main-group element
Main group element
In chemistry and atomic physics, main group elements are elements in groups whose lightest members are represented by helium, lithium,...
centers, Martin and Arduengo devised the N-X-L nomenclature system. The synthesis and characterization of the first compound with a planar T-shaped, 10-electron
Electron
The electron is a subatomic particle with a negative elementary electric charge. It has no known components or substructure; in other words, it is generally thought to be an elementary particle. An electron has a mass that is approximately 1/1836 that of the proton...
3-coordinate bonding arrangement at a phosphorus
Phosphorus
Phosphorus is the chemical element that has the symbol P and atomic number 15. A multivalent nonmetal of the nitrogen group, phosphorus as a mineral is almost always present in its maximally oxidized state, as inorganic phosphate rocks...
atom, ADPO, was also accomplished by the Arduengo group at Illinois and paved the way for a range of novel main-group element
Main group element
In chemistry and atomic physics, main group elements are elements in groups whose lightest members are represented by helium, lithium,...
chemistry (including the discovery of edge inversion) on his return to DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
. The final Illinois research extended the newly discovered ADPO chemistry to the arsenic analog (ADAsO).
DuPont 1984-1999
On returning to DuPontDuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
in 1984, Arduengo resumed a position in CR&D
DuPont Central Research
In 1957, the research organization of the Chemicals Department of E. I. du Pont de Nemours and Company was renamed Central Research Department, beginning the history of the premier scientific organization within DuPont and one of the foremost industrial laboratories devoted to basic science...
and continued the research into the recently discovered ADPO molecule and related structures. This line of research proved to be extremely fruitful and resulted in a steady string of publications on new and unusual bonding arrangements. The ADPO related chemistry provided a basis for the discovery of a new inverson process, edge inverson, which was fully characterized and modelled by the collaborative work of Arduengo and David A. Dixon at DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
. Additionally, the DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
team provided experimental verification on the new inversion pathway at 3-coordinate phosphorus
Phosphorus
Phosphorus is the chemical element that has the symbol P and atomic number 15. A multivalent nonmetal of the nitrogen group, phosphorus as a mineral is almost always present in its maximally oxidized state, as inorganic phosphate rocks...
centers and a 4-coordinate germanium molecule.
Arduengo's work with DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
also involved a number of applied projects including the flexible polyimide
Polyimide
Polyimide is a polymer of imide monomers. The structure of imide is as shown. Polyimides have been in mass production since 1955...
film, Kapton
Kapton
Kapton is a polyimide film developed by DuPont which can remain stable in a wide range of temperatures, from -273 to +400 °C...
®-ZT, that is widely used in electronics for flexible printed circuits, connections, and insulation. Arduengo's research at DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
often coalesced with his other hobbies outside the laboratory; for example with sports cars (cf. photo in the summary box above). He contributed to development of low VOC
Volatile organic compound
Volatile organic compounds are organic chemicals that have a high vapor pressure at ordinary, room-temperature conditions. Their high vapor pressure results from a low boiling point, which causes large numbers of molecules to evaporate or sublimate from the liquid or solid form of the compound and...
automotive coatings by devising catalysts for a novel cross-link
Cross-link
Cross-links are bonds that link one polymer chain to another. They can be covalent bonds or ionic bonds. "Polymer chains" can refer to synthetic polymers or natural polymers . When the term "cross-linking" is used in the synthetic polymer science field, it usually refers to the use of...
ing chemistry used by DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
Performance Coatings in next-generation low-VOC
Volatile organic compound
Volatile organic compounds are organic chemicals that have a high vapor pressure at ordinary, room-temperature conditions. Their high vapor pressure results from a low boiling point, which causes large numbers of molecules to evaporate or sublimate from the liquid or solid form of the compound and...
paints. Eventually, DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
waterborne performance coatings would be used by Lotus
Lotus Cars
Lotus Cars is a British manufacturer of sports and racing cars based at the former site of RAF Hethel, a World War II airfield in Norfolk. The company designs and builds race and production automobiles of light weight and fine handling characteristics...
on their Elise
Lotus Elise
The 1996 Lotus Elise weighed . Because of its relatively low weight, it was able to accelerate 0- in 5.8 seconds despite its relatively low power output of...
and Exige
Lotus Exige
The Lotus Exige is a two-door, two-seat sports car made by Lotus Cars. It is essentially a coupé version of the Lotus Elise, a mid-engined roadster in production since 1996....
models. Arduengo's effort on the industrial-scale syntheses of the catalysts for the paints on which he worked would launch his re-entry into the area of carbene
Carbene
In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is RR'C:, but the carbon can instead be double-bonded to one group. The term "carbene" may also merely refer to the compound H2C:, also called...
chemistry, but this time it was to be nucleophilic
Nucleophile
A nucleophile is a species that donates an electron-pair to an electrophile to form a chemical bond in a reaction. All molecules or ions with a free pair of electrons can act as nucleophiles. Because nucleophiles donate electrons, they are by definition Lewis bases.Nucleophilic describes the...
rather than electrophilic
Electrophile
In general electrophiles are positively charged species that are attracted to an electron rich centre. In chemistry, an electrophile is a reagent attracted to electrons that participates in a chemical reaction by accepting an electron pair in order to bond to a nucleophile...
carbenes. The observation that the catalyst syntheses were well tolerant of varied reaction conditions and substituents led Arduengo to postulate that the imidazol-2-ylidenes that were intermediates
Reactive intermediate
In chemistry a reactive intermediate is a short-lived, high energy, highly reactive molecule. When generated in a chemical reaction it will quickly convert into a more stable molecule. Only in exceptional cases can these compounds be isolated and stored, e.g. low temperatures, matrix isolation...
in the syntheses had to be far more stable than the then conventional wisdom would allow.
As Arduengo's involvement in the automotive coatings program came to an end, he submitted a proposal to the management in CR&D
DuPont Central Research
In 1957, the research organization of the Chemicals Department of E. I. du Pont de Nemours and Company was renamed Central Research Department, beginning the history of the premier scientific organization within DuPont and one of the foremost industrial laboratories devoted to basic science...
to isolated these apparently stable carbenes and study their chemistry. The proposal was soundly declined with the admonition that he should have certainly known better than to make such a suggestion in light of the long history of carbene
Carbene
In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is RR'C:, but the carbon can instead be double-bonded to one group. The term "carbene" may also merely refer to the compound H2C:, also called...
chemistry that firmly established them as reactive intermediate
Reactive intermediate
In chemistry a reactive intermediate is a short-lived, high energy, highly reactive molecule. When generated in a chemical reaction it will quickly convert into a more stable molecule. Only in exceptional cases can these compounds be isolated and stored, e.g. low temperatures, matrix isolation...
s that could not be isolated as stable entities. However, Arduengo (already well-aware of the history) had the starting materials on hand for the chemistry and decided to proceed with the experiments. “Arduengo’s gamble paid off. In 1991, more than 150 years after the first attempt ...” a stable crystalline carbene was isolated and characterized in laboratories at DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
. After the first successful reaction to produce a stable carbene
Persistent carbene
A persistent carbene is a type of carbene demonstrating particular stability. The best-known examples are diaminocarbenes with the general formula 2C:, where the 'R's are various functional groups...
, Arduengo won the support of DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
management and research in this area continued. Carbenes bearing a variety of substituent groups were prepared and characterized. The saturated imidazolin-2-ylidenes
Dihydroimidazol-2-ylidene
Dihydroimidazol-2-ylidene is a hypothetical organic compound with formula C3H6N2. It would be a heterocyclic compound, formally derived from imidazolidine with two hydrogen atoms removed from carbon number 2, leaving two vacant chemical bonds — which makes it a carbene.Although carbenes in general...
that were extensively investigated by Hans-Werner Wanzlick
Hans-Werner Wanzlick
Hans-Werner Wanzlick was a professor of chemistry at the Berlin Technical University. He is notable for work on persistent carbenes and for proposing the Wanzlick equilibrium between saturated imidazolin-2-ylidenes and their dimers — which he called "das doppelte Lottchen", after a 1949 novel by...
thirty years earlier (without isolation) were now also shown to be stable enough to isolate with appropriate substituents at nitrogen. An air-stable carbene was produced. The chemistry was extended to include thiazol-2-ylidenes (conjectured to exist in 1957 as a reactive intermediate
Reactive intermediate
In chemistry a reactive intermediate is a short-lived, high energy, highly reactive molecule. When generated in a chemical reaction it will quickly convert into a more stable molecule. Only in exceptional cases can these compounds be isolated and stored, e.g. low temperatures, matrix isolation...
in the vitamin B1 catalytic cycle
Catalytic cycle
A catalytic cycle in chemistry is a term for a multistep reaction mechanism that involves a catalyst . The catalytic cycle is the main method for describing the role of catalysts in biochemistry, organometallic chemistry, materials science, etc. Often such cycles show the conversion of a...
, but not isolated for 40 years). The imidazol-2-ylidenes were extensively characterized by their NMR
Nuclear magnetic resonance
Nuclear magnetic resonance is a physical phenomenon in which magnetic nuclei in a magnetic field absorb and re-emit electromagnetic radiation...
properties, photo-electron spectroscopy
Ultraviolet photoelectron spectroscopy
Ultraviolet photoelectron spectroscopy refers to the measurement of kinetic energy spectra of photoelectrons emitted by molecules which have absorbed ultraviolet photons, in order to determine molecular energy levels in the valence region.-Basic Theory:...
, and exact experimental electron density mapping by X-ray
X-ray crystallography
X-ray crystallography is a method of determining the arrangement of atoms within a crystal, in which a beam of X-rays strikes a crystal and causes the beam of light to spread into many specific directions. From the angles and intensities of these diffracted beams, a crystallographer can produce a...
and neutron diffraction
Neutron diffraction
Neutron diffraction or elastic neutron scattering is the application of neutron scattering to the determination of the atomic and/or magnetic structure of a material: A sample to be examined is placed in a beam of thermal or cold neutrons to obtain a diffraction pattern that provides information of...
techniques.
The Arduengo group's characterization of stable carbene
Persistent carbene
A persistent carbene is a type of carbene demonstrating particular stability. The best-known examples are diaminocarbenes with the general formula 2C:, where the 'R's are various functional groups...
s was complemented by a wide ranging exploration of their chemistry. This new chemistry included carbene
Carbene
In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is RR'C:, but the carbon can instead be double-bonded to one group. The term "carbene" may also merely refer to the compound H2C:, also called...
reactions with numerous element centers including iodine
Iodine
Iodine is a chemical element with the symbol I and atomic number 53. The name is pronounced , , or . The name is from the , meaning violet or purple, due to the color of elemental iodine vapor....
, aluminum, copper
Copper
Copper is a chemical element with the symbol Cu and atomic number 29. It is a ductile metal with very high thermal and electrical conductivity. Pure copper is soft and malleable; an exposed surface has a reddish-orange tarnish...
, silver
Silver
Silver is a metallic chemical element with the chemical symbol Ag and atomic number 47. A soft, white, lustrous transition metal, it has the highest electrical conductivity of any element and the highest thermal conductivity of any metal...
, magnesium
Magnesium
Magnesium is a chemical element with the symbol Mg, atomic number 12, and common oxidation number +2. It is an alkaline earth metal and the eighth most abundant element in the Earth's crust and ninth in the known universe as a whole...
, zinc
Zinc
Zinc , or spelter , is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2...
, germanium
Germanium
Germanium is a chemical element with the symbol Ge and atomic number 32. It is a lustrous, hard, grayish-white metalloid in the carbon group, chemically similar to its group neighbors tin and silicon. The isolated element is a semiconductor, with an appearance most similar to elemental silicon....
, nickel
Nickel
Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile...
, platinum
Platinum
Platinum is a chemical element with the chemical symbol Pt and an atomic number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little silver of the Pinto River." It is a dense, malleable, ductile, precious, gray-white transition metal...
, lanthanide
Lanthanide
The lanthanide or lanthanoid series comprises the fifteen metallic chemical elements with atomic numbers 57 through 71, from lanthanum through lutetium...
s, and hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
in the form a bis(carbene)-proton complex. Arduengo's research from 1996 also reflects his interaction with his host for his Alexander von Humboldt Research Prize
Humboldt Prize
The Humboldt Prize, also known as the Humboldt Research Award, is an award given by the Alexander von Humboldt Foundation to internationally renowned scientists and scholars, and is currently valued at € 60,000 with the possibility of further support during the prize winner's life. Up to one...
, Professor Reinhard Schmutzler. His carbene
Carbene
In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is RR'C:, but the carbon can instead be double-bonded to one group. The term "carbene" may also merely refer to the compound H2C:, also called...
chemistry conducted from Braunschweig included reactivity studies of imidazol-2-ylidenes with fluorinated inorganic compounds. New structures included carbene•phenyltetrafluorophosphorane, carbene•PF5, carbene•AsF5, carbene•SbF5, and carbene•BF3 adducts. Arduengo's final work on carbene
Carbene
In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is RR'C:, but the carbon can instead be double-bonded to one group. The term "carbene" may also merely refer to the compound H2C:, also called...
s at DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
included synthesis and characterization of carbene·alkaline earth metal
Alkaline earth metal
The alkaline earth metals are a group in the periodic table. In the modern IUPAC nomenclature, the alkaline earth metals are called the group 2 elements. Previously, they were called the Group IIA elements . The alkaline earth metals contain beryllium , magnesium , calcium , strontium , barium and...
, carbene•antimony
Antimony
Antimony is a toxic chemical element with the symbol Sb and an atomic number of 51. A lustrous grey metalloid, it is found in nature mainly as the sulfide mineral stibnite...
, carbene•cadmium
Cadmium
Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, bluish-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Similar to zinc, it prefers oxidation state +2 in most of its compounds and similar to mercury it shows a low...
, and carbene•lithium
Lithium
Lithium is a soft, silver-white metal that belongs to the alkali metal group of chemical elements. It is represented by the symbol Li, and it has the atomic number 3. Under standard conditions it is the lightest metal and the least dense solid element. Like all alkali metals, lithium is highly...
adducts. Reactions of carbene
Carbene
In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is RR'C:, but the carbon can instead be double-bonded to one group. The term "carbene" may also merely refer to the compound H2C:, also called...
s with phosphinidene
Phosphinidene
Phosphinidenes in chemistry are chemical compounds containing a monovalent and diradical phosphorus atom. They are the phosphorus analogs of carbenes and nitrenes. The parent compound is phosphinidene...
s were also reported from Arduengo's laboratory in addition to insertion reactions of imidazolin-2-ylidenes
Dihydroimidazol-2-ylidene
Dihydroimidazol-2-ylidene is a hypothetical organic compound with formula C3H6N2. It would be a heterocyclic compound, formally derived from imidazolidine with two hydrogen atoms removed from carbon number 2, leaving two vacant chemical bonds — which makes it a carbene.Although carbenes in general...
.
In 1998, Arduengo and coworkers carefully re-examined the earlier attempts to produce stable carbenes in Wanzlick's laboratory in light of the knowledge and experience gained from the recent successful experiments at DuPont. Although the majority of Wanzlick's work on the saturated imidazolin-2-ylidenes
Dihydroimidazol-2-ylidene
Dihydroimidazol-2-ylidene is a hypothetical organic compound with formula C3H6N2. It would be a heterocyclic compound, formally derived from imidazolidine with two hydrogen atoms removed from carbon number 2, leaving two vacant chemical bonds — which makes it a carbene.Although carbenes in general...
would have been expected to yield dimers in the absence of bulky substituents on nitrogen, a single (unsaturated) imidazol-2-ylidene, 1,3,4,5-tetraphenylimidazol-2-ylidene, remained as an example of a carbene that could (should) have been isolable. The re-examination of Wanzlick's original procedure identified some key experimental features that would have hindered the original researchers. With these problems corrected, the DuPont scientists were able to isolate the target carbene and fully characterize it including an X-ray structure determination. In a tribute to Hans-Werner Wanzlick, these results were published under the title “1,3,4,5-Tetraphenylimidazol-2-ylidene: The Realization of Wanzlick's Dream.”
University of Alabama 1999-present
At the University of Alabama research from Arduengo's laboratory has focused on enhancements to the basic structure of the imidazol-2-ylidenes through substituent effects leading to novel compounds like a cyclopentadienylCyclopentadiene
Cyclopentadiene is an organic compound with the formula C5H6. This colorless liquid has a strong and unpleasant odor. At room temperature, this cyclic diene dimerizes over the course of hours to give dicyclopentadiene via a Diels–Alder reaction...
fused imidazol-2-ylidene. Research into the unusual valency in diphosphacyclobutane-2,4-diyls has been reported from the Arduengo group in collaboration with Professors Masaaki Yoshifuji and Shigekazu Ito. Arduengo also directs research programs into Chemical Hydrogen Storage and nonlinear optical material
Nonlinear optics
Nonlinear optics is the branch of optics that describes the behavior of light in nonlinear media, that is, media in which the dielectric polarization P responds nonlinearly to the electric field E of the light...
s.
Awards
- Fellow of the American Association for the Advancement of ScienceAmerican Association for the Advancement of ScienceThe American Association for the Advancement of Science is an international non-profit organization with the stated goals of promoting cooperation among scientists, defending scientific freedom, encouraging scientific responsibility, and supporting scientific education and science outreach for the...
, October 2007 - Walter J. Chute Lectureship 1999-2000.
- Gold Medal for "Excellence in Main Group Chemistry Research" from The International Council on Main Group Chemistry, 1996
- Alexander von Humboldt Senior Research PrizeHumboldt PrizeThe Humboldt Prize, also known as the Humboldt Research Award, is an award given by the Alexander von Humboldt Foundation to internationally renowned scientists and scholars, and is currently valued at € 60,000 with the possibility of further support during the prize winner's life. Up to one...
, 1996 - NSFNational Science FoundationThe National Science Foundation is a United States government agency that supports fundamental research and education in all the non-medical fields of science and engineering. Its medical counterpart is the National Institutes of Health...
Undergraduate Fellowship, 1972, 1973