Du Pont Central Research - Organometallic Chemistry

Organometallic Chemistry

Cramer’s Dimer
Tebbe Reagent

CRD developed a major interest in inorganic and organometallic chemistry. Earl Muetterties established a program aimed at fundamental borane chemistry. Walter Knoth discovered the first polyhedral borane anion, B10H10=, and also discovered that the borane anions displayed a substitution chemistry similar to that of aromatic hydrocarbons. Norman Miller discovered the B12H12= anion in an effort to find a new route to B10H10=. George Parshall joined CRD in 1954. His industrial sabbatical at Imperial College London with Geoffrey Wilkinson in 1960-61 introduced him to organometallic chemistry. Muetterties left DuPont to join the faculty of Cornell in 1973. After Muetterties and Parshall, the organometallic chemistry group was led by Steven Ittel and then Henry Bryndza before it was dispersed throughout a number of groups in CRD. Parshall and Ittel coauthored a book on “Homogeneous Catalysis” that has become the standard reference on the subject.

The seminal contributions of Richard Cramer and Fred Tebbe are acknowledged by their named compounds, “Cramer’s dimer,” Rh2Cl2(C2H4)4, and the “Tebbe reagent.” Tebbe had an influence on his lab partner, Richard Schrock who initiated a program on M=C chemistry at DuPont and continued it when he moved to MIT. The chemistry forms the basis for olefin metathesis, and Schrock ultimately shared the Nobel Prize with Robert Grubbs, a CRD consultant, for the metathesis work. Anthony Arduengo’s persistent carbenes opened up a new area of chemistry and they have proven to be important ligands in the metathesis process.

There was a vigorous effort on the activation of C-H bonds with contributions by Parshall, Thomas Herskovitz, Ittel, and David Thorn. Chad Tolman developed his “ligand cone angle” theory that developed into the widely accepted electronic and steric effects of ligands on inorganic and organometallic complexes.

Organometallic chemistry in CRD has further included R. Thomas Baker's heterobinuclear complexes, Patricia L. Watson's organolanthanides, William A. Nugent's metal-ligand multiple bonds, Jeffery Thompson's and Mani Subramanyam's development of technetium complexes for radiopharmaceuticals, and Bob Burch's and Karin Karel's fluoro-organometallic chemistry. The major outlet for organometallic chemistry is homogeneous catalysis. DuPont developed a major technology based upon the nickel catalyzed addition of two molecules of hydrogen cyanide to butadiene, giving adiponitrile, a nylon intermediate. The mechanistic work to provide an understanding of the technology was done in CRD and led to a large program on next-generation technology before the business was sold to Koch Industries. Other applications of homogeneous catalysis studied in CRD include ethylene polymerization, cyclohexane oxidation to adipic acid, and butadiene carbonylation to nylon intermediates. Approaches to catalyst systems have included homogeneous organometallic catalysts, heterobinuclear catalysts, polyoxometalates, enzymes, catalytic membrane reactors and supported organometallics.

Read more about this topic:  Du Pont Central Research

Other articles related to "organometallic chemistry, chemistry":

Organometallic Chemistry - Organometallics
... Period 2 elements organolithium chemistry, organoberyllium chemistry, organoborane chemistry, Period 3 elements organomagnesium chemistry, organoaluminum chemistry, organosilicon ... organopalladium chemistry, organosilver chemistry, organocadmium chemistry, organoindium chemistry, organotin chemistry Period 6 elements ...
F. Gordon A. Stone - Academic Life
... two years, before being appointed as an instuctor in the Chemistry Department at Harvard University, and was appointed assistant professor in 1957 ... Welch Distinguished Professor of Chemistry at Baylor University, Texas until 2010, but his most productive period was as Professor of Inorganic Chemistry at Bristol University, England (1963–1990 ... Elected to the Royal Society of Chemistry in 1970, and to the Royal Society in 1976, he was awarded the Davy Medal "In recognition of his many ...
Malcolm Green (chemist)
... Green (born 16 April 1936) is a British Emeritus Professor of Inorganic Chemistry ... became a Septcentenary Fellow of Inorganic Chemistry at Balliol College and a Departmental Demonstrator at the University of Oxford ... In 1989 he was appointed Professor of Inorganic Chemistry and Head of the Inorganic Chemistry Laboratory at Oxford and Fellow of St Catherine’s College ...
Maurice Brookhart
... Professor of Chemistry (1990 to the present) in the Department of Chemistry at the University of North Carolina ... North Carolina Residence United States Citizenship United States Fields Organometallic chemistry Institutions University of North Carolina at Chapel Hill 1969-Present Postdoctoral ... Johnson(Postdoc) Known for Mechanisms in organometallic chemistry Notable awards ACS Award in Organometallic Chemistry (1992) North Carolina Section ACS Distinguished Speaker Award (1992 ...

Famous quotes containing the word chemistry:

    For me chemistry represented an indefinite cloud of future potentialities which enveloped my life to come in black volutes torn by fiery flashes, like those which had hidden Mount Sinai. Like Moses, from that cloud I expected my law, the principle of order in me, around me, and in the world.... I would watch the buds swell in spring, the mica glint in the granite, my own hands, and I would say to myself: “I will understand this, too, I will understand everything.”
    Primo Levi (1919–1987)