David Milstein
Encyclopedia
David Milstein is an Israeli chemist best known for his research on metal-mediated activation and functionalization of very strong chemical bonds.
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”.
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
.
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. 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. This paper is considered a classic for establishing a general strategy for C-C activation in homogeneous systems. 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.
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.
Using the same pincer-like ruthenium catalyst, Milstein and co-workers devised a new method for making amides, based on coupling alcohols and amines. This research was selected by Science magazine as one of the top ten breakthroughs of 2007, 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.
Foundation, 2011
• Fellow of the Royal Society of Chemistry
, 2010
• The 2010 Royal Society of Chemistry Sir Geoffrey Wilkinson Award http://www.rsc.org/ScienceAndTechnology/Awards/SirGeoffreyWilkinsonAward/2010Winner.asp
• The 2007 American Chemical Society
Award in Organometallic Chemistry
• Research selected by Science among the top 10 major scientific breakthroughs of the year 2007 http://www.sciencemag.org/cgi/content/full/318/5858/1844a
• 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)
• 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).
Biography
Milstein, who immigrated with his family to the newly founded state of IsraelIsrael
The State of Israel is a parliamentary republic located in the Middle East, along the eastern shore of the Mediterranean Sea...
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
Rehovot
Rehovot is a city in the Center District of Israel, about south of Tel Aviv. According to the Israel Central Bureau of Statistics , at the end of 2009 the city had a total population of 112,700. Rehovot's official website estimates the population at 114,000.Rehovot was built on the site of Doron,...
where “an enthusiastic, old-fashioned chemistry teacher who didn’t care much about orbitals” inspired him “with vivid, thought-provoking experiments”.
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
Weizmann Institute of Science
The Weizmann Institute of Science , known as Machon Weizmann, is a university and research institute in Rehovot, Israel. It differs from other Israeli universities in that it offers only graduate and post-graduate studies in the sciences....
in Israel, where he is now director of the Kimmel Center for Molecular Design and the Israel Matz Professorial Chair of Organic Chemistry
Organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, composition, reactions, and preparation of carbon-based compounds, hydrocarbons, and their derivatives...
.
Research
Milstein has authored Over 220 publications in peer-reviewed journals . 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
John Kenneth Stille
John Kenneth Stille was an American chemist who discovered the Stille reaction. He received B.A and M.A. degrees from the University of Arizona and his Ph.D. at the University of Illinois, where he met his wife-to-be Dolores Engelking...
, discovered the Stille reaction
Stille reaction
The Stille reaction is a chemical reaction coupling an organotin compound with an sp2-hybridized organic halide catalyzed by palladium. The reaction is widely used in organic synthesis....
for new carbon-carbon bond
Carbon-carbon bond
A carbon–carbon bond is a covalent bond between two carbon atoms. The most common form is the single bond: a bond composed of two electrons, one from each of the two atoms. The carbon–carbon single bond is a sigma bond and is said to be formed between one hybridized orbital from each...
formation using a palladium catalyst to couple an organic halide with an organotin compound. 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. This paper is considered a classic for establishing a general strategy for C-C activation in homogeneous systems. 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.
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
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...
using a pincer-type ruthenium catalyst.
Using the same pincer-like ruthenium catalyst, Milstein and co-workers devised a new method for making amides, based on coupling alcohols and amines. This research was selected by Science magazine as one of the top ten breakthroughs of 2007, 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
Renewable energy
Renewable energy is energy which comes from natural resources such as sunlight, wind, rain, tides, and geothermal heat, which are renewable . About 16% of global final energy consumption comes from renewables, with 10% coming from traditional biomass, which is mainly used for heating, and 3.4% from...
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.
Honors and awards
• The Humboldt Research Award by the Alexander Von HumboldtAlexander von Humboldt
Friedrich Wilhelm Heinrich Alexander Freiherr von Humboldt was a German naturalist and explorer, and the younger brother of the Prussian minister, philosopher and linguist Wilhelm von Humboldt...
Foundation, 2011
• Fellow of the Royal Society of Chemistry
Royal Society of Chemistry
The Royal Society of Chemistry is a learned society in the United Kingdom with the goal of "advancing the chemical sciences." It was formed in 1980 from the merger of the Chemical Society, the Royal Institute of Chemistry, the Faraday Society and the Society for Analytical Chemistry with a new...
, 2010
• The 2010 Royal Society of Chemistry Sir Geoffrey Wilkinson Award http://www.rsc.org/ScienceAndTechnology/Awards/SirGeoffreyWilkinsonAward/2010Winner.asp
• The 2007 American Chemical Society
American Chemical Society
The American Chemical Society is a scientific society based in the United States that supports scientific inquiry in the field of chemistry. Founded in 1876 at New York University, the ACS currently has more than 161,000 members at all degree-levels and in all fields of chemistry, chemical...
Award in Organometallic Chemistry
• Research selected by Science among the top 10 major scientific breakthroughs of the year 2007 http://www.sciencemag.org/cgi/content/full/318/5858/1844a
• 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).