Электронная книга: David Milstein «Ligand Design in Metal Chemistry. Reactivity and Catalysis»

Ligand Design in Metal Chemistry. Reactivity and Catalysis

The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub-discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting-edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: Key concepts in ligand design Redox non-innocent ligands Ligands for selective alkene metathesis Ligands in cross-coupling Ligand design in polymerization Ligand design in modern lanthanide chemistry Cooperative metal-ligand reactivity P,N Ligands for enantioselective hydrogenation Spiro-cyclic ligands in asymmetric catalysis This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry, polymer science and materials chemistry.

Издательство: "John Wiley&Sons Limited"

ISBN: 9781118839775

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David Milstein

David Milstein is an Israeli chemist best known for his research on metal-mediated activation and functionalization of very strong chemical bonds.

David Milstein
Born 4 June 1947 (1947-06-04) (age 64)
Ulm, Germany
Nationality Israel, United States
Fields Organometallic chemistry
Alma mater The Hebrew University
Known for Metal-mediated activation of chemical bonds.

Contents

Biography

Milstein, who immigrated with his family to the newly founded state of Israel at the age of two, was born (1947) in the city of Ulm, in post-war Germany, where his family took refuge after being displaced during the Holocaust. Milstein was first fascinated by chemistry when attending high school in the town of Rehovot where “an enthusiastic, old-fashioned chemistry teacher who didn’t care much about orbitals” inspired him “with vivid, thought-provoking experiments”.[1] Pursuing his interest, Milstein received B.Sc., M.Sc., and Ph.D. degrees in chemistry from the Hebrew University of Jerusalem. He carried out postdoctoral research in the U.S. at the University of Iowa and at Colorado State University. In 1979, Milstein joined DuPont Central Research & Development in Wilmington, Delaware, where he became a group leader in the homogeneous catalysis area. In 1987, he took up an academic position at the Weizmann Institute of Science in Israel, where he is now director of the Kimmel Center for Molecular Design and the Israel Matz Professorial Chair of Organic Chemistry.

Research

Milstein has authored Over 220 publications in peer-reviewed journals [1]. He and his coworkers have developed many group 8, 9, and 10 transition-metal complexes with specifically designed ligands that have proven useful to activate strong C-C, C-H, C-F, N-H, and O-H bonds.

The C-C Bond

While a postdoc, Milstein and his adviser, John Kenneth Stille, discovered the Stille reaction for new carbon-carbon bond formation using a palladium catalyst to couple an organic halide with an organotin compound.[2] This reaction is considered a very useful method for new C-C bond formation and is now widely used in the synthesis of pharmaceuticals. His subsequent research on the C-C bond includes a 1993 publication describing insertion of a rhodium complex into a strong C-C bond using a pincer-type substrate that helps draw the metal center to the hard-to-access C-C bond.[3] This paper is considered a classic for establishing a general strategy for C-C activation in homogeneous systems.[4] Milstein's research focused also on bonds between carbon and other elements. An example is his work on activation of the notoriously inert C-F bond in reactions of fluorinated benzenes with silanes or hydrogen using a rhodium catalyst.[5]

New Route to Amide Synthesis

Milstein had dealt in his research with N-H and O-H activation, inserting iridium complexes into the N-H bond of ammonia and the O-H bond of water and converting primary alcohols to esters with liberation of hydrogen using a pincer-type ruthenium catalyst.[6] Using the same pincer-like ruthenium catalyst, Milstein and co-workers devised a new method for making amides, based on coupling alcohols and amines.[7] This research was selected by Science magazine as one of the top ten breakthroughs of 2007,[8] being praised both for its cleanliness and selectivity, eschewing the harsh reagents and conditions usually required to make amides and creating H2 gas as the only by-product.

Light-induced Water Splitting

Discovery of an efficient artificial catalyst for the sunlight-driven splitting of water is a major goal of renewable energy research, as it would allow generation of energy-dense hydrogen without investment of electricity. Recently, Milstein and his co-workers have described a solution-phase reaction scheme that leads to the stoichiometric liberation of hydrogen and oxygen in consecutive thermal- and light-driven steps mediated by mononuclear, well-defined ruthenium complexes, in essence establishing a new light-driven water splitting strategy that does not require a sacrificial chemical in the process.[9][10]

Honors and awards

• The Humboldt Research Award by the Alexander Von Humboldt Foundation, 2011

• Fellow of the Royal Society of Chemistry, 2010

• The 2010 Royal Society of Chemistry Sir Geoffrey Wilkinson Award [2]

• The 2007 American Chemical Society Award in Organometallic Chemistry

• Research selected by Science among the top 10 major scientific breakthroughs of the year 2007 [3]

• The 2006 Israel Chemical Society Prize

• Election to the German Academy of Sciences Leopoldina, 2006

• Miller Visiting Professor, Miller Institute, UC Berkeley, spring 2006

• The I.M. Kolthoff Prize in Chemistry, 2002 (awarded by Technion, Israel Institute of Technology)

• The Paolo Chini Memorial Award 1999 (awarded by the Italian Chemical Society)

Major publications

• A general, selective, and facile method for ketone synthesis from acid chlorides and organotin compounds catalyzed by palladium, D. Milstein, J. K. Stille. J. Am. Chem. Soc. 100 (11), 3636 – 3638 (1978).

• Activation of a carbon–carbon bond in solution by transition-metal insertion, M. Gozin, A. Weisman, Y. Ben-David, D. Milstein. Nature 364, 699 - 701 (1993).

• Transfer of methylene groups promoted by metal complexation, M. Gozin, M. Aizenberg, S.-Y. Liou, A. Weisman, Y. Ben-David, D. Milstein, Nature 370, 42 - 44 (1994).

• Catalytic activation of carbon-fluorine bonds by a soluble transition metal complex, M. Aizenberg, D. Milstein. Science 265, 359 – 361 (1994).

• Impact of molecular order in Langmuir-Blodgett films on catalysis,K. Tollner, R. Popovitz-Biro, M. Lahav, D. Milstein, Science, 278, 2100 - 2102 (1997).

• Facile conversion of alcohols into esters and dihydrogen catalyzed by new ruthenium complexes, J. Zhang, G. Leitus, Y. Ben-David, D. Milstein. J. Am. Chem. Soc. 127, 10840 − 10841 (2005).

• Direct synthesis of amides from alcohols and amines with liberation of H2, C. Gunanathan, Y. Ben-David, D. Milstein Science 2007, 317, 790 - 792 (2007).

• Evidence for a terminal Pt(IV)-oxo complex exhibiting diverse reactivity, E. Poverenov, I. Efremenko, A. I. Frenkel, Y. Ben-David, L. J. W. Shimon, G. Leitus, L. Konstantinovski, J. M. L. Martin, D. Milstein, Nature 455, 1093 - 1096 (2008)

• Consecutive thermal H2 and light-induced O2 evolution from water promoted by a metal complex, S. W. Kohl, L. Weiner, L. Schwartsburd, L. Konstantinovski, L. J. W. Shimon, Y. Ben-David, M. A. Iron, D. Milstein, Science,324, 74-77 (2009).

Personal

Son of Musia and Abraham and younger brother of Lea, Milstein married to Adi Milstein in 1971, with whom he has three children: Nofit (b. 1972), Oren (b. 1976), and Abraham (b. 1983). He resides in the town of Rehovot in Israel.

References

Источник: David Milstein

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