Assignment Tokoh Organometallic Gilman
Assignment Tokoh Organometallic Gilman
HENRY
GILMAN
In 1919, Dr. Gilman recalls, the chemistry program at Iowa State was “very modest - 15 or
18 undergraduate majors and perhaps a dozen graduate students. But there was a nice esprit de
corps. They were young and enthusiastic. They all worked quite hard. And Dr. Henry Gilman had
a nice, easy, personal relationship with the students.” The hard work, the esprit de corps and the
results were recognized and in 1923 he was named professor of organic chemistry at Iowa State.
Within six months of his arrival at Iowa State, Professor Gilman submitted his first of many papers
dealing with the Grignard reagent, influenced perhaps by the interests of his Harvard mentor,
Professor E.P. Kohler. Beginning at a time when Iowa State had little financial support for
research, Professor Gilman has made contributions so enormous - over 1000 articles, books, and
chapters in books bear his name - that a brief summary cannot
treat them justly. The principal themes have been heterocyclic
chemistry and organometallic chemistry.
However, Professor Gilman’s first and continuing love has been organometallic chemistry.
Starting from a few scattered observations in the literature and inspired by the Grignard reagent
studies, he developed that branch of science now known as organometallic chemistry. His research
papers describe the organic chemistry of aluminum, arsenic, barium, beryllium, bismuth,
cadmium, calcium, copper, gallium, germanium, gold, iridium, lead, lithium, magnesium,
mercury, phosphorus, platinum, potassium, selenium, silicon, silver, sodium, thallium, tin,
uranium and zinc. His initial interest in organomagnesiurn chemistry led to extensive studies of
organolithium compounds. This pioneering research made possible the wide use of these versatile
reagents in organic synthesis and provided the background for the preparation of polymers such
as polyethylene and cis-polyisoprene.
Through the years, many other honors and awards have come to Professor Gilman. He was
elected to the National Academy of Science in 1945. In 1951, he received two American Chemical
Society awards: the Iowa Award and the Midwest Award. He has been selected as Fellow of the
Chemical Society (London), a signal honor limited to forty persons. At Iowa State, the chemistry
building has been named Henry Gilman Hall and the annual Gilman Lectures were initiated in
1914. For many years, Professor Gilman has been an international leader in the organic chemistry
of silicon and his fundamental discoveries in this field contributed to the development of silicone
polymers and many related industrial products. His many and outstanding contributions to the
organosilicon field were acknowledged when, in 1962, he was named the first recipient of the
American Chemical Society’s Frederic Stanley Kipping Award in Organosilicon Chemistry. In
1976, he was one of three foreign scientists to be elected to honorary membership in the British
Royal Society. The following year, 1977, he was presented the American Chemical Society’s
Priestly Medal “for distinguished services to chemistry”; this gold medal is considered the highest
honor in U.S. chemistry.
During his lifetime, Gilman completed 1020 papers, 584 of which were published after he
became blind in 1947. In 1936, the Journal of Organic Chemistry was created by Gilman with the
help of M.S. Kharasch. In 1938, he published a two-volume textbook titled Organic Chemistry:
An Advanced Treatise, the first major organic chemistry textbook, with each chapter being
contributed by leading leaders in the U.S. Subsequent additions were published in 1943 and
another two editions in 1953. Gilman reagents are named after him.
Gilman’s research interests have focused on “unnatural products”, that is, organometallic
compounds that must be prepared and manipulated in the absence of air and moisture. Some of his
most important individual discoveries have also involved “unnatural chemical behavior”, by a
given element. For example, the halogen-lithium exchange process (eq. l), which was discovered,
independently, by Gilman and by Wittig in 1938 shows that the nonmetallic halogens can behave
like metals in being exchanged for them. He rightly judged that the average organic chemist
overestimated the experimental difficulties in working with organometallics and underassessed
their value. A sampling of his efforts to correct this false impression is worth listing: (1) the
preparation of hydrocarbons from the coupling of alkyl sulfonates and Grignard reagents, (2) the
conjugate addition of Grignard reagents to a,β-unsaturated anils, (3) the formation of ketones from
RLi and R’COOLi, (4) the preparation of organocuprates, R,CuLi, (5) the preparation of ketones
from R2Cd and R’COX, the use of tetrahydrofuran to accelerate hydrogen-lithium exchanges and
the preparation of organolithium reagents from the cleavage of ethers and sulfides in THF.
Conversely, in his pioneering research on triorganosilylmetallic compounds (R3 Si - M+, eq. 2),
Gilman demonstrated that the metalloid, silicon, could exhibit nonmetallic traits very similar to
those of carbon (R3 C – M +, eq. 3):
This change in the apparent polarity of an atom in certain bonding situations has been designated
in recent years. Gilman’s work provides some of the earliest, most telling examples. Although the
hydrogen-lithium exchange was not discovered by Gilman (eq. 4), he expanded its scope almost
beyond recognition to encompass RH substrates of
little discernible acidity. This work drew upon another of his abiding research themes, namely the
substitution chemistry of oxygen- and nitrogen-containing heterocycles. With these substrates
Gilman developed novel substitution processes based on hydrogen-lithium exchange, which led to
nuclear substitution different from conventional substitution processes (eq. 5).
This unique synthetic approach was also applied by Gilman to derivatives of furan,
dibenzothiophene, phenothiazine, carbazole, pyridines, quinolines and acridines and has led to a
host of compounds of value as pesticides, herbicides, antimalarials, anti-infective and
antidepressants. Very recently, the role of such lithiations in heterocyclic synthesis has taken on
great importance.
During the latter half of his career, Gilman devoted a steadily increasing effort to the
chemistry of organosilicon compounds having two or more silicon atoms in a chain or ring. In
devising the various synthetic routes to such unusual compounds, in assessing the chemical
reactivity of the Si-Si bond and in developing reliable methods for structure determination, Gilman
achieved the pioneering crest of his productive life. The Tetrakis(trimethylsilyl)silane is one of
many organosilicon compounds first reported by Gilman et al.
Figure 1 Tetrakis (trimethylsilyl)silane, (TMS)
In recognition of this, he was named the first recipient of the Frederic Stanley Kipping Award in
Organosilicon Chemistry in 1962. All in all, threading through all these broader research themes
was Gilman’s continual interest in useful applications of organometallic reagents for organic
synthesis, here are the list of awards receive by this scientist:
Professor Gilman’s former students speak of him with respect and affection. He has often,
and with some justification, been referred to as a stem taskmaster who demanded hard work and
perfection from his students; but he asked no more than he was willing to give. A research director
at one of our large chemical companies once remarked that he found that former Gilman students
not only knew their chemistry but also had been taught precision in chemical reporting. Professor
Gilman is a person of highest integrity with a strong sense of ethics; these attributes were also part
of the “Gilman training.”
While demanding and unyielding on a professional level, Professor Gilman was always
kind, thoughtful and helpful to his students on a personal level. He would loan money and arrange
medical care or legal assistance when needed. He was always available for personal advice when
his students were having difficulties. In addition, he has been ever helpful to his students and
former students in finding suitable employment, making a change in employment and arranging
for postdoctoral studies, especially studies abroad. One former student has written to Professor
Gilman: “You probably are bored with eulogies about your contributions to chemistry. But how
many people realize what a lovely lob you had in tennis? Or what a fantastic left hand you played
in handball? Or what a delightful conversationalist you can be?” Indeed, Dr. Gilman is superb at
conversation - articulate and knowledgeable in many areas, a good story teller but also a good
listener. In group conversations there may be one person who is quiet and not participating; in such
situations Professor Gilman has often been observed to stop, turn, and ask just the right question
to make sure all are included. Throughout his career, Professor Gilman has been known for his
splendid lectures, beautifully delivered with an absence of lecture notes.
In 1947, due to a combination of glaucoma and detachment of a retina Henry Gilman
became blind in one eye and lost most of his vision in the other. He was forced to rely on his wife
and students to act as his eyes, to read and write for him. His wife was almost always at his side to
guide him in unfamiliar places and inform him of the people around him. Remarkably, he
continued much of his work and never let his loss of sight hinder his skills. It could be argued that
the majority of Gilman’s work was done after 1947. In 1973, the current chemistry building at
Iowa State University was renamed Henry Gilman Hall.
REFERENCES
Eaborn, C. (1990). "Henry Gilman. 9 May 1893-7 November 1986". Biographical Memoirs of
Fellows of the Royal Society. 36: 152. doi:10.1098/rsbm.1990.0028.
Eisch, John J. (2002). "Henry Gilman: American Pioneer in the Rise of Organometallic Chemistry
in Modern Science and Technology". Organometallics. 21 (25): 5439–5463.
doi:10.1021/om0109408.