Kenichi Fukui

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Kenichi Fukui
Kenichi Fukui.jpg
BornOctober 4, 1918
DiedJanuary 9, 1998 (aged 79)
Kyoto, Japan
NationalityJapan
Citizenship Japan
Alma mater Kyoto Imperial University
Known for Frontier orbitals [1]
Spouse(s)Tomoe Horie (m.1947)
Children2
Awards
Scientific career
Fields Chemistry
Institutions Kyoto University

Kenichi Fukui (福井 謙一 Fukui Ken'ichi, October 4, 1918 – January 9, 1998) was a Japanese chemist, [2] known as the first Asian scientist to receive a chemistry Nobel Prize.

Japan Constitutional monarchy in East Asia

Japan is an island country in East Asia. Located in the Pacific Ocean, it lies off the eastern coast of the Asian continent and stretches from the Sea of Okhotsk in the north to the East China Sea and the Philippine Sea in the south.

Chemist scientist trained in the study of chemistry

A chemist is a scientist trained in the study of chemistry. Chemists study the composition of matter and its properties. Chemists carefully describe the properties they study in terms of quantities, with detail on the level of molecules and their component atoms. Chemists carefully measure substance proportions, reaction rates, and other chemical properties. The word 'chemist' is also used to address Pharmacists in Commonwealth English.

Nobel Prize Set of annual international awards, primarily 5 established in 1895 by Alfred Nobel

The Nobel Prize is a set of annual international awards bestowed in several categories by Swedish and Norwegian institutions in recognition of academic, cultural, or scientific advances.

Contents

Professor Fukui was co-recipient of the Nobel Prize in Chemistry in 1981 with Roald Hoffmann, for their independent investigations into the mechanisms of chemical reactions. His prize-winning work focused on the role of frontier orbitals in chemical reactions: specifically that molecules share loosely bonded electrons which occupy the frontier orbitals, that is the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO). [3] [4] [5] [6] [7] [8] [9]

Nobel Prize in Chemistry One of the five Nobel Prizes established in 1895 by Alfred Nobel

The Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature, peace, and physiology or medicine. This award is administered by the Nobel Foundation, and awarded by Royal Swedish Academy of Sciences on proposal of the Nobel Committee for Chemistry which consists of five members elected by Academy. The award is presented in Stockholm at an annual ceremony on December 10, the anniversary of Nobel's death.

Roald Hoffmann Nobel laureate organic and inorganic chemist and Holocaust child survivor

Roald Hoffmann is a Polish-American theoretical chemist who won the 1981 Nobel Prize in Chemistry. He has also published plays and poetry. He is the Frank H. T. Rhodes Professor of Humane Letters, Emeritus, at Cornell University, in Ithaca, New York.

Early life

Fukui was the eldest of three sons of Ryokichi Fukui, a foreign trade merchant, and Chie Fukui. He was born in Nara, Japan. In his student days between 1938 and 1941, Fukui's interest was stimulated by quantum mechanics and Erwin Schrödinger's famous equation. He also had developed the belief that a breakthrough in science occurs through the unexpected fusion of remotely related fields.

Quantum mechanics branch of physics dealing with phenomena at scales of the order of the Planck constant

Quantum mechanics, including quantum field theory, is a fundamental theory in physics which describes nature at the smallest scales of energy levels of atoms and subatomic particles.

Erwin Schrödinger 20th-century Austrian physicist

Erwin Rudolf Josef Alexander Schrödinger, sometimes written as Erwin Schrodinger or Erwin Schroedinger, was a Nobel Prize-winning Austrian physicist who developed a number of fundamental results in the field of quantum theory: the Schrödinger equation provides a way to calculate the wave function of a system and how it changes dynamically in time.

In an interview with The Chemical Intelligencer Kenichi discusses his path towards chemistry starting from middle school.

"The reason for my selection of chemistry is not easy to explain, since chemistry was never my favorite branch in middle school and high school years. Actually, the fact that my respected Fabre had been a genius in chemistry had captured my heart latently, the most decisive occurrence in my education career came when my father asked the advice of Professor Gen-itsu Kita of the Kyoto Imperial University concerning the cause I should take.”

On the advice of Kita, a personal friend of the elder Fukui, young Kenichi was directed to the Department of Industrial Chemistry, with which Kita was then affiliated. He also explains that chemistry was difficult to him because it seemed to require memorization to learn it, and that he preferred more logical character in chemistry. He followed the advice a mentor that was well respected by Kenichi himself and never looked back. He also followed in those footsteps by attending Kyoto University in Japan. During that same interview Kenichi also discussed his reason for preferring more theoretical chemistry rather than experimental chemistry. Although he certainly acceded at theoretical science he actually spent much of his early research on experimental. Kenichi had quickly completed more than 100 experimental projects and papers, and he rather enjoyed the experimental phenomena of chemistry. In fact, later on when teaching he would recommend experimental thesis projects for his students to balance them out, theoretical science came more natural to students, but by suggesting or assigning experimental projects his students could understand the concept of both, as all scientist should. Following his graduation from Kyoto Imperial University in 1941, Fukui was engaged in the Army Fuel Laboratory of Japan during World War II. In 1943, he was appointed a lecturer in fuel chemistry at Kyoto Imperial University and began his career as an experimental organic chemist.

Kyoto University national university located in Kyoto, Japan

Kyoto University, or Kyodai is a national university in Kyoto, Japan. It is the second oldest Japanese university, one of Asia's highest ranked universities and one of Japan's National Seven Universities. One of Asia’s leading research-oriented institutions, Kyoto University is famed for producing world-class researchers, including 18 Nobel Prize laureates, 2 Fields medalists and one Gauss Prize winner. It has the most Nobel laureates of all universities in Asia.

World War II 1939–1945 global war

World War II, also known as the Second World War, was a global war that lasted from 1939 to 1945. The vast majority of the world's countries—including all the great powers—eventually formed two opposing military alliances: the Allies and the Axis. A state of total war emerged, directly involving more than 100 million people from over 30 countries. The major participants threw their entire economic, industrial, and scientific capabilities behind the war effort, blurring the distinction between civilian and military resources. World War II was the deadliest conflict in human history, marked by 50 to 85 million fatalities, most of whom were civilians in the Soviet Union and China. It included massacres, the genocide of the Holocaust, strategic bombing, premeditated death from starvation and disease, and the only use of nuclear weapons in war.

Research

Kenichi Fukui Monument at Kyoto University Kenichi Fukui Monument at Kyoto University.JPG
Kenichi Fukui Monument at Kyoto University

He was professor of physical chemistry at Kyoto University from 1951 to 1982, president of the Kyoto Institute of Technology between 1982 and 1988, and a member of the International Academy of Quantum Molecular Science and honorary member of the International Academy of Science.[ citation needed ] He was also director of the Institute for Fundamental Chemistry from 1988 till his death. As well as President of the Chemical Society of Japan from 1983–84, receiving multiple awards aside from his Nobel Prize such as; Japan Academy Prize in 1962, Person of Cultural Merit in 1981, Imperial Honour of Grand Cordon of the Order of the Rising Sun in 1988, with many other awards not quite as prestigious.

Kyoto Institute of Technology university

Kyoto Institute of Technology in Kyoto, Japan is a Japanese national university established in 1949. The Institute's history extends back to two schools, Kyoto Craft High School and Kyoto Sericulture Training School, which were forerunners of the Faculty of Engineering and Design and the Faculty of Textile Science, respectively. The former was moved to Sakyo-ku, Matsugasaki in 1930 and changed its name to Kyoto Industrial High School in 1944. The latter developed into Kyoto Sericulture High School, under supervision of the Ministry of Education in 1914, and changed its name to Kyoto Sericulture Technical High School in 1931 and then to Kyoto Technical High School of Sericulture in 1944. The two forerunners merged in 1949, due to educational system revisions, to establish the present School of Science and Technology. Together with Shinshu University and Tokyo University of Agriculture and Technology, the Institute is one of Japan's three historical centers of textile research.

The International Academy of Quantum Molecular Science (IAQMS) is an international scientific learned society covering all applications of quantum theory to chemistry and chemical physics. It was created in Menton in 1967. The founding members were Raymond Daudel, Per-Olov Löwdin, Robert G. Parr, John Pople and Bernard Pullman. Its foundation was supported by Louis de Broglie.

In 1952, Fukui with his young collaborators T. Yonezawa and H. Shingu presented his molecular orbital theory of reactivity in aromatic hydrocarbons, which appeared in the Journal of Chemical Physics . At that time, his concept failed to garner adequate attention among chemists. Fukui observed in his Nobel lecture in 1981 that his original paper 'received a number of controversial comments. This was in a sense understandable, because for lack of my experiential ability, the theoretical foundation for this conspicuous result was obscure or rather improperly given.'

The frontier orbitals concept came to be recognized following the 1965 publication by Robert B. Woodward and Roald Hoffmann of the Woodward-Hoffmann stereoselection rules, which could predict the reaction rates between two reactants. These rules, depicted in diagrams, explain why some pairs react easily while other pairs do not. The basis for these rules lies in the symmetry properties of the molecules and especially in the disposition of their electrons. Fukui had acknowledged in his Nobel lecture that, 'It is only after the remarkable appearance of the brilliant work by Woodward and Hoffmann that I have become fully aware that not only the density distribution but also the nodal property of the particular orbitals have significance in such a wide variety of chemical reactions.'

What has been striking in Fukui's significant contributions is that he developed his ideas before chemists had access to large computers for modeling. Apart from exploring the theory of chemical reactions, Fukui's contributions to chemistry also include the statistical theory of gelation, organic synthesis by inorganic salts and polymerization kinetics.

In an interview to New Scientist magazine in 1985, Fukui had been highly critical on the practices adopted in Japanese universities and industries to foster science. He noted, "Japanese universities have a chair system that is a fixed hierarchy. This has its merits when trying to work as a laboratory on one theme. But if you want to do original work you must start young, and young people are limited by the chair system. Even if students cannot become assistant professors at an early age they should be encouraged to do original work." Fukui also admonished Japanese industrial research stating, "Industry is more likely to put its research effort into its daily business. It is very difficult for it to become involved in pure chemistry. There is a need to encourage long-range research, even if we don't know its goal and if its application is unknown." In another interview with The Chemical Intelligencer he further elaborates on his criticism by saying, "As is known worldwide, Japan has tried to catch up with the western countries since the beginning of this century by importing science from them." Japan is, in a sense, relatively new to fundamental science as a part of its society and the lack of originality ability, and funding which the western countries have more advantages in hurt the country in fundamental science. Although, he has also stated that it is improving in Japan, especially funding for fundamental science as it has seen a steady increase for years.

Recognition

Fukui was awarded the Nobel Prize for his realization that a good approximation for reactivity could be found by looking at the frontier orbitals (HOMO/LUMO). This was based on three main observations of molecular orbital theory as two molecules interact.

  1. The occupied orbitals of different molecules repel each other.
  2. Positive charges of one molecule attract the negative charges of the other.
  3. The occupied orbitals of one molecule and the unoccupied orbitals of the other (especially HOMO and LUMO) interact with each other causing attraction.

From these observations, frontier molecular orbital (FMO) theory simplifies reactivity to interactions between HOMO of one species and the LUMO of the other. This helps to explain the predictions of the Woodward-Hoffman rules for thermal pericyclic reactions, which are summarized in the following statement: "A ground-state pericyclic change is symmetry-allowed when the total number of (4q+2)s and (4r)a components is odd" [10] [11] [12] [13]

Fukui was elected a Foreign Member of the Royal Society (ForMemRS) in 1989. [2]

See also

Related Research Articles

In organic chemistry, the Diels–Alder reaction is a chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile, to form a substituted cyclohexene derivative. It is the prototypical example of a pericyclic reaction with a concerted mechanism. More specifically, it is classified as a thermally-allowed [4+2] cycloaddition with Woodward–Hoffmann symbol [π4s + π2s]. It was first described by Otto Diels and Kurt Alder in 1928. For the discovery of this reaction, they were awarded the Nobel Prize in Chemistry in 1950. Through the simultaneous construction of two new carbon–carbon bonds, the Diels–Alder reaction provides a reliable way to form six-membered rings with good control over the regio- and stereochemical outcomes. Consequently, it has served as a powerful and widely applied tool for the introduction of chemical complexity in the synthesis of natural products and new materials. The underlying concept has also been applied to π-systems involving heteroatoms, such as carbonyls and imines, which furnish the corresponding heterocycles; this variant is known as the hetero-Diels–Alder reaction. The reaction has also been generalized to other ring sizes, although none of these generalizations have matched the formation of six-membered rings in terms of scope or versatility. Because of the negative values of ΔH° and ΔS° for a typical Diels–Alder reaction, the microscopic reverse of a Diels–Alder reactions becomes favorable at high temperatures, although this is of synthetic importance for only a limited range of Diels-Alder adducts, generally with some special structural features; this reverse reaction is known as the retro-Diels–Alder reaction.

Dudley R. Herschbach American chemist

Dudley Robert Herschbach is an American chemist at Harvard University. He won the 1986 Nobel Prize in Chemistry jointly with Yuan T. Lee and John C. Polanyi "for their contributions concerning the dynamics of chemical elementary processes." Herschbach and Lee specifically worked with molecular beams, performing crossed molecular beam experiments that enabled a detailed molecular-level understanding of many elementary reaction processes. Herschbach is a member of the Board of Sponsors of the Bulletin of the Atomic Scientists.

Yuan T. Lee Taiwanese chemist

Yuan Tseh Lee is a Taiwanese chemist and a Professor Emeritus at the University of California, Berkeley. He was the first Taiwanese Nobel Prize laureate who, along with the Hungarian-Canadian John C. Polanyi and American Dudley R. Herschbach, won the Nobel Prize in Chemistry in 1986 "for their contributions to the dynamics of chemical elementary processes".

Robert Burns Woodward American chemist

Robert Burns Woodward was an American organic chemist. He is considered by many to be the preeminent organic chemist of the twentieth century, having made many key contributions to the subject, especially in the synthesis of complex natural products and the determination of their molecular structure. He also worked closely with Roald Hoffmann on theoretical studies of chemical reactions. He was awarded the Nobel Prize in Chemistry in 1965.

HOMO/LUMO

In chemistry, HOMO and LUMO are types of molecular orbitals. The acronyms stand for highest occupied molecular orbital and lowest unoccupied molecular orbital, respectively.

Isolobal principle

The isolobal principle is a strategy used in organometallic chemistry to relate the structure of organic and inorganic molecular fragments in order to predict bonding properties of organometallic compounds. Roald Hoffmann described molecular fragments as isolobal "if the number, symmetry properties, approximate energy and shape of the frontier orbitals and the number of electrons in them are similar – not identical, but similar." One can predict the bonding and reactivity of a lesser-known species from that of a better-known species if the two molecular fragments have similar frontier orbitals, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Isolobal compounds are analogues to isoelectronic compounds that share the same number of valence electrons and structure. A graphic representation of isolobal structures, with the isolobal pairs connected through a double-headed arrow with half an orbital below, is found in Figure 1.

The 1,3-dipolar cycloaddition is a chemical reaction between a 1,3-dipole and a dipolarophile to form a five-membered ring. The earliest 1,3-dipolar cycloadditions were described in the late 19th century to the early 20th century, following the discovery of 1,3-dipoles. Mechanistic investigation and synthetic application were established in the 1960s, primarily through the work of Rolf Huisgen. Hence, the reaction is sometimes referred to as the Huisgen cycloaddition. 1,3-dipolar cycloaddition is an important route to the regio- and stereoselective synthesis of five-membered heterocycles and their ring-opened acyclic derivatives.

An electrocyclic reaction can either be classified as conrotatory or disrotatory based on the rotation at each end of the molecule. In conrotatory mode, both atomic orbitals of the end groups turn in the same direction. In disrotatory mode, the atomic orbitals of the end groups turn in opposite directions. The cis/trans geometry of the final product is directly decided by the difference between conrotation and disrotation.

Woodward–Hoffmann rules

The Woodward–Hoffmann rules, devised by Robert Burns Woodward and Roald Hoffmann, are a set of rules used to rationalize or predict certain aspects of the stereochemistry and activation energy of pericyclic reactions, an important class of reactions in organic chemistry. The Woodward–Hoffmann rules are a consequence of the changes in electronic structure that occur during a pericyclic reaction and are predicated on the phasing of the interacting molecular orbitals. They are applicable to all classes of pericyclic reactions, including (1) electrocyclizations, (2) cycloadditions, (3) sigmatropic reactions, (4) group transfer reactions, (5) ene reactions, (6) cheletropic reactions, and (7) dyotropic reactions. Due to their elegance, simplicity, and generality, the Woodward–Hoffmann rules are credited with first exemplifying the power of molecular orbital theory to experimental chemists.

Antibonding molecular orbital type of molecular orbital (MO) that weakens the bond between two atoms and helps to raise the energy of the molecule relative to the separated atom; is normally higher in energy than bonding molecular orbital

In chemical bonding theory, an antibonding orbital is a type of molecular orbital (MO) that weakens the chemical bond between two atoms and helps to raise the energy of the molecule relative to the separated atoms. Such an orbital has one or more nodes in the bonding region between the nuclei. The density of the electrons in the orbital is concentrated outside the bonding region and acts to pull one nucleus away from the other and tends to cause mutual repulsion between the two atoms. This is in contrast to a bonding molecular orbital, which has a lower energy than that of the separate atoms, and is responsible for chemical bonds.

Physical organic chemistry, a term coined by Louis Hammett in 1940, refers to a discipline of organic chemistry that focuses on the relationship between chemical structures and reactivity, in particular, applying experimental tools of physical chemistry to the study of organic molecules. Specific focal points of study include the rates of organic reactions, the relative chemical stabilities of the starting materials, reactive intermediates, transition states, and products of chemical reactions, and non-covalent aspects of solvation and molecular interactions that influence chemical reactivity. Such studies provide theoretical and practical frameworks to understand how changes in structure in solution or solid-state contexts impact reaction mechanism and rate for each organic reaction of interest.

A non-bonding orbital, also known as non-bonding molecular orbital (NBMO), is a molecular orbital whose occupation by electrons neither increases nor decreases the bond order between the involved atoms. Non-bonding orbitals are often designated by the letter n in molecular orbital diagrams and electron transition notations. Non-bonding orbitals are the equivalent in molecular orbital theory of the lone pairs in Lewis structures. The energy level of a non-bonding orbital is typically in between the lower energy of a valence shell bonding orbital and the higher energy of a corresponding antibonding orbital. As such, a non-bonding orbital with electrons would commonly be a HOMO.

In chemistry, frontier molecular orbital theory is an application of MO theory describing HOMO/LUMO interactions.

Walsh diagram

Walsh diagrams, often called angular coordinate diagrams or correlation diagrams, are representations of calculated orbital binding energies of a molecule versus a distortion coordinate, used for making quick predictions about the geometries of small molecules. By plotting the change in molecular orbital levels of a molecule as a function of geometrical change, Walsh diagrams explain why molecules are more stable in certain spatial configurations.

The Inverse electron demand Diels–Alder reaction, or DAINV or IEDDA is an organic chemical reaction, in which two new chemical bonds and a six-membered ring are formed. It is related to the Diels–Alder reaction, but unlike the Diels–Alder reaction, the DAINV is a cycloaddition between an electron-rich dienophile and an electron-poor diene. During a DAINV reaction, three pi-bonds are broken, and two sigma bonds and one new pi-bond are formed. A prototypical DAINV reaction is shown on the right.

In computational chemistry, the Fukui function or frontier function is a function that describes the electron density in a frontier orbital, as a result of a small change in the total number of electrons. The condensed Fukui function or condensed reactivity indicator is the same idea, but applied to an atom within a molecule, rather than a point in three-dimensional space.

A metal-centered cycloaddition is a subtype of the more general class of cycloaddition reactions. In such reactions "two or more unsaturated molecules unite directly to form a ring", incorporating a metal bonded to one or more of the molecules. Cycloadditions involving metal centers are a staple of organic and organometallic chemistry, and are involved in many industrially-valuable synthetic processes.

In the theory of chemical reactivity, the Klopman-Salem equation describes the energetic change that occurs when two species approach each other in the course of a reaction and begin to interact, as their associated molecular orbitals begin to overlap with each other and atoms bearing partial charges begin to experience attractive or repulsive electrostatic forces. First described independently by Gilles Klopman and Lionel Salem in 1968, this relationship provides a mathematical basis for the key assumptions of frontier molecular orbital theory and hard soft acid base (HSAB) theory. Conceptually, it highlights the importance of considering both electrostatic interactions and orbital interactions when rationalizing the selectivity or reactivity of a chemical process.

Trisilaallene class of chemical compounds

Trisilaallene is a subclass of silene derivatives where a central silicon atom forms double bonds with each of two terminal silicon atoms, with the generic formula R2Si=Si=SiR2. Trisilaallene is a silicon-based analog of an allene, but their chemical properties are markedly different.

References

  1. "Fukui's Frontiers: The first Japanese scientist to win a Nobel Prize introduced the concept of frontier orbitals" (PDF). Pubs.acs.org. Retrieved 2015-11-09.
  2. 1 2 3 Buckingham, A. D.; Nakatsuji, H. (2001). "Kenichi Fukui. 4 October 1918 -- 9 January 1998: Elected F.R.S. 1989". Biographical Memoirs of Fellows of the Royal Society . 47: 223. doi:10.1098/rsbm.2001.0013.
  3. Fukui, K (November 1982). "Role of Frontier Orbitals in Chemical Reactions". Science . 218 (4574): 747–754. Bibcode:1982Sci...218..747F. doi:10.1126/science.218.4574.747. PMID   17771019.
  4. Fukui, K.; Yonezawa, T.; Shingu, H. (1952). "A Molecular Orbital Theory of Reactivity in Aromatic Hydrocarbons". The Journal of Chemical Physics. 20 (4): 722. Bibcode:1952JChPh..20..722F. doi:10.1063/1.1700523.
  5. Bell J, Johnstone B, Nakaki S: The new face of Japanese science. New Scientist, March 21, 1985, p. 31.
  6. Sri Kantha S: Kenichi Fukui. In, Biographical Encyclopedia of Scientists, edited by Richard Olson, Marshall Cavendish Corp, New York, 1998, pp. 456–458. [ ISBN missing ]
  7. The Chemical Intelligencer 1995, 1(2), 14-18, Springer-Verlag, New York, Inc.
  8. "Biographical Snapshots | Chemical Education Xchange". Jce.divched.org. Retrieved 2015-11-09.
  9. "Kenichi Fukui – Biographical". Nobelprize.org. Retrieved 2015-11-09.
  10. Theory of orientation and stereoselection (1975), ISBN   978-3-642-61917-5
  11. An Einstein dictionary, Greenwood Press, Westport, CT, by Sachi Sri Kantha ; foreword contributed by Kenichi Fukui (1996), ISBN   0-313-28350-8
  12. Frontier orbitals and reaction paths : selected papers of Kenichi Fukui (1997) ISBN   978-981-02-2241-3
  13. The science and technology of carbon nanotubes edited by Kazuyoshi Tanaka, Tokio Yamabe, Kenichi Fukui (1999), ISBN   978-0080426969