History of Organometallic Chemistry 7
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1 Introduction to Early Main Group Organometallic Chemistry and Catalysis
1 1 Introduction to Early Main Group Organometallic Chemistry and Catalysis Sjoerd Harder University Erlangen-Nürnberg, Inorganic and Organometallic Chemistry, Egerlandstrasse 1, 91058 Erlangen, Germany 1.1 Introduction Although organometallic complexes of the early main groups are well known for their very high reactivity and challenging isolation, they are among the first stud- ied during the pioneering beginnings of the field. Their high nucleophilicity and Brønsted basicity have made them to what they are today: strong polar reagents that are indispensible in modern organic synthesis. It is exactly this high reactivity that has made them potent catalysts for organic transformations that are gener- ally catalyzed by transition metal complexes. Despite their lack of partially filled d-orbitals and their inability to switch reversibly between oxidation states, the scope of their application in catalysis is astounding. As the early main group metal catalysis only started to become popular since the beginning of this century, it is still a young field with ample opportunities for further development. This intro- ductory chapter is specifically written for new graduate students in the field. It gives a very compact overview of the history of early main group organometallic chemistry, synthetic methods, bonding and structures, analytical methods, solu- tion dynamics, and some preliminary low-valent chemistry. This forms the basis for understanding their use in catalysis for which the basic steps are described in the second part of this chapter. For further in-depth information, the reader is referred to the individual chapters in this book. 1.2 s-Block Organometallics 1.2.1 Short History The organometallic chemistry of the highly electropositive early main group metals could not have started without the isolation of these elements in the metallic state. -
Geoffrey Wilkinson
THE LONG SEARCH FOR STABLE TRANSITION METAL ALKYLS Nobel Lecture, December 11, 1973 by G EOFFREY W ILKINSON Imperial College of Science & Technology, London, England Chemical compounds in which there is a single bond between a saturated car- bon atom and a transition metal atom are of unusual importance. Quite aside from the significance and role in Nature of the cobalt to carbon bonds in the vitamin B 12 system and possible metal to carbon bonds in other biological systems, we need only consider that during the time taken to deliver this lec- ture, many thousands, if not tens of thousands of tons of chemical compounds are being transformed or synthesised industrially in processes which at some stage involve a transition metal to carbon bond. The nonchemist will pro- bably be most familiar with polyethylene or polypropylene in the form of do- mestic utensils, packaging materials, children’s toys and so on. These materials are made by Ziegler-Natta* or Philipps’ catalysis using titanium and chro- mium respectively. However, transition metal compounds are used as catalysts in the synthesis of synthetic rubbers and other polymers, and of a variety of simple compounds used as industrial solvents or intermediates. For example alcohols are made from olefins, carbon monoxide and hydrogen by use of cobalt or rhodium catalysts, acetic acid is made by carbonylation of methanol using rhodium catalysts and acrylonitrile is dimerised to adiponitrile (for nylon) by nickel catalysts. We should also not forget that the huge quantities of petroleum hydrocarbons processed by the oil and petrochemical industry are re-formed over platinum, platinum-rhenium or platinum-germanium sup- ported on alumina. -
Goverdhan Mehta Chemistry - a 21St Century Science for Global Sustainability: Is It Future Ready?
Goverdhan Mehta Chemistry - A 21st Century Science for Global Sustainability: Is it future ready? Goverdhan Mehta A ‘selfie’ with theSchool chemical of Chemistry world…… University of Hyderabad National Geophysical Research Institute, CSIR Foundation Day, Sept. 27, 2019 Introducing Chemistry through the Lens of Earth's Systems: What Role Can Systems Thinking Play in Developing Chemically and Environmentally Literate Citizens? J. Kornfeld, S. Stokoe. J. Chemical Education 2019, 96, 2910-2917 A bouquet of ‘matters’ that matter New symbols Passion Sustainability Legacies Ethics & values Responsible Connections Systems Directions Humility Ideas & icons Inspirations Un mélange de beaucoup de choses “Chemistry ought not to be for chemists alone” - Miguel de Unamuno ‘…Life, Universe and Everything’ Chemistry – a source of happiness…. Chem -Connectome ‘...I feel sorry for people who don’t know anything about chemistry. They are missing an important source of happiness....’ - Linus Pauling 1901-1994 S.A. Matlin, G. Mehta, H. Hopf. Chemistry Embraced by All. Science 2015, 347, 1179 Chemistry is in everything. and everything is in it, it is the basis of life, without it we wouldn't exist. Green tea has ~ 200 chemicals Coffee has ~ 1000 chemicals Wine has >1000 chemicals Light cigarette ~ 4000 chemicals Chemistry is ubiquitous/omnipresent Chemistry – Tracing the roots and to the present BCE Art & craft of mixing substances A giant knowledge leap Alchemy to modern science Evidence based science Discipline in a Table - systematization Mendeleev’s Periodic Law ‘Molecularization’ of chemical matter 20th Century A century of evolutionary march of chemistry 20h Century Value added products from almost anything “Utility science” and everything Molecular understanding of life processes and “Core Science” chemical matter Interdisciplinarity in forefront “Integrative Science” Resource stressed planet “Sustainability Science” 21st Century S. -
Fischer Carbene Complexes in Organic Synthesis Ke Chen 1/31/2007
Baran Group Meeting Fischer Carbene Complexes in Organic Synthesis Ke Chen 1/31/2007 Ernst Otto Fischer (1918 - ) Other Types of Stabilized Carbenes: German inorganic chemist. Born in Munich Schrock carbene, named after Richard R. Schrock, is nucleophilic on November 10, 1918. Studied at Munich at the carbene carbon atom in an unpaired triplet state. Technical University and spent his career there. Became director of the inorganic Comparision of Fisher Carbene and Schrock carbene: chemistry institute in 1964. In the 1960s, discovered a metal alkylidene and alkylidyne complexes, referred to as Fischer carbenes and Fischer carbynes. Shared the Nobel Prize in Chemistry with Geoffery Wilkinson in 1973, for the pioneering work on the chemistry of organometallic compounds. Schrock carbenes are found with: Representatives: high oxidation states Isolation of first transition-metal carbene complex: CH early transition metals Ti(IV), Ta(V) 2 non pi-acceptor ligands Cp2Ta CH N Me LiMe Me 2 2 non pi-donor substituents CH3 (CO) W CO (CO)5W 5 (CO)5W A.B. Charette J. Am. Chem. Soc. 2001, 123, 11829. OMe O E. O. Fischer, A. Maasbol, Angew. Chem. Int. Ed., 1964, 3, 580. Persistent carbenes, isolated as a crystalline solid by Anthony J. Arduengo in 1991, can exist in the singlet state or the triplet state. Representative Fischer Carbenes: W(CO) Cr(CO) 5 5 Fe(CO)4 Mn(CO)2(MeCp) Co(CO)3SnPh3 Me OMe Ph Ph Ph NEt2 Ph OTiCp2Cl Me OMe Foiled carbenes were defined as "systems where stabilization is Fischer carbenes are found with : obtained by the inception of the facile reaction which is foiled by the impossibility of attaining the final product geometry". -
1 Introduction
1 Field-control, phase-transitions, and life’s emergence 2 3 4 Gargi Mitra-Delmotte 1* and A.N. Mitra 2* 5 6 7 139 Cite de l’Ocean, Montgaillard, St.Denis 97400, REUNION. 8 e.mail : [email protected] 9 10 2Emeritius Professor, Department of Physics, Delhi University, INDIA; 244 Tagore Park, 11 Delhi 110009, INDIA; 12 e.mail : [email protected] 13 14 15 16 17 18 19 *Correspondence: 20 Gargi Mitra-Delmotte 1 21 e.mail : [email protected] 22 23 A.N. Mitra 2 24 e.mail : [email protected] 25 26 27 28 29 30 31 32 33 34 35 Number of words: ~11748 (without Abstract, references, tables, and figure legends) 36 7 figures (plus two figures in supplementary information files). 37 38 39 40 41 42 43 44 45 46 47 Abstract 48 49 Critical-like characteristics in open living systems at each organizational level (from bio- 50 molecules to ecosystems) indicate that non-equilibrium phase-transitions into absorbing 51 states lead to self-organized states comprising autonomous components. Also Langton’s 52 hypothesis of the spontaneous emergence of computation in the vicinity of a critical 53 phase-transition, points to the importance of conservative redistribution rules, threshold, 54 meta-stability, and so on. But extrapolating these features to the origins of life, brings up 55 a paradox: how could simple organics-- lacking the ‘soft matter’ response properties of 56 today’s complex bio-molecules--have dissipated energy from primordial reactions 57 (eventually reducing CO 2) in a controlled manner for their ‘ordering’? Nevertheless, a 58 causal link of life’s macroscopic irreversible dynamics to the microscopic reversible laws 59 of statistical mechanics is indicated via the ‘functional-takeover’ of a soft magnetic 60 scaffold by organics (c.f. -
Iron-Catalysed Transformation of Molecular Dinitrogen Into Silylamine Under Ambient Conditions
ARTICLE Received 6 Sep 2012 | Accepted 6 Nov 2012 | Published 4 Dec 2012 DOI: 10.1038/ncomms2264 Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions Masahiro Yuki1, Hiromasa Tanaka2, Kouitsu Sasaki1, Yoshihiro Miyake1, Kazunari Yoshizawa2 & Yoshiaki Nishibayashi1 Although stoichiometric transformations using transition metal–N2 complexes have been well investigated towards the goal of nitrogen fixation under mild reaction conditions, only a few examples of the catalytic transformations of N2 using transition metal–N2 complexes as catalysts have been reported. In almost all the catalytic systems, the use of Mo is essential to realize the catalytic transformation of N2, where Mo–N2 complexes are considered to work as effective catalysts. Here we show the first successful example of the Fe-catalysed transfor- mation of N2 into N(SiMe3)3 under ambient conditions, in which iron complexes such as iron pentacarbonyl [Fe(CO)5] and ferrocenes have been found to work as effective catalysts. A plausible reaction pathway is proposed, where Fe(II)–N2 complex bearing two Me3Si groups as ancillary ligands has an important role as a key reactive intermediate, with the aid of density-functional-theory calculations. 1 Institute of Engineering Innovation, School of Engineering, University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan. 2 Institute for Materials Chemistry and Engineering, International Research Center for Molecular Systems, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan. Correspondence and requests for materials should be addressed to K.Y. (email: [email protected]) or to Y.N. (email: [email protected]). -
Bimetallic Catalyst Catalyzed Carbonylation of Methanol to Acetic Acid
materials Article Study on Rh(I)/Ru(III) Bimetallic Catalyst Catalyzed Carbonylation of Methanol to Acetic Acid Shasha Zhang 1, Wenxin Ji 1,2,*, Ning Feng 2, Liping Lan 1, Yuanyuan Li 1,2 and Yulong Ma 1,2 1 College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China; [email protected] (S.Z.); [email protected] (L.L.); [email protected] (Y.L.); [email protected] (Y.M.) 2 State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, China; [email protected] * Correspondence: [email protected]; Tel.: +86-135-1957-9989; Fax: +86-951-206-2323 Received: 13 July 2020; Accepted: 3 September 2020; Published: 11 September 2020 Abstract: In this study, a Rh(I)/Ru(III) catalyst with a bimetallic space structure was designed and synthesized. The interaction between the metals of the bimetallic catalyst and the structure of the bridged dimer can effectively reduce the steric hindrance effect and help speed up the reaction rate while ensuring the stability of the catalyst. X-ray photoelectron spectroscopy (XPS) results show that rhodium accepts electrons from chlorine, thereby increasing the electron-rich nature of rhodium and improving the catalytic activity. This promotes the nucleophilic reaction of the catalyst with methyl iodide and reduces the reaction energy barrier. The methanol carbonylation performance of the Rh/Ru catalyst was evaluated, and the results show that the conversion rate of methyl acetate and the yield of acetic acid are 96.0% under certain conditions. Furthermore, during the catalysis, no precipitate is formed and the amount of water is greatly reduced. -
Advances in the Carbonylation of Aryl Halides Using Palladium Catalysts
FIRST SOLVIAS SCIENCE DAY 684 CHIMIA 2001,55, No.9 Chimia 55 (2001) 684--687 © Schweizerische Chemische Gesellschaft ISSN 0009-4293 Advances in the Carbonylation of Aryl Halides Using Palladium Catalysts Matthias Bellera* and Adriano F. Indoleseb Abstract: The palladium-catalyzed carbonylation of aryl halides is shown to be a versatile tool for the synthesis of various benzoic and heteroaromatic acid derivatives. Recent developments from our laboratories in this area are presented. Keywords: Benzoic acid derivatives· Carbonylation . Homogeneous catalysis· Palladium Introduction From a general point of view the leav- Elegant work by researchers from ing group of the aryl-X derivative is for- Hoffmann-La Roche also demonstrated Palladium-catalyzed carbonylation reac- mally replaced by a nucleophile with in- the industrial applicability of such a reac- tions of aryl-X compounds leading to corporation of one or two molecules of tion in the commercial process for carboxylic acid derivatives were estab- CO (Scheme I). In addition to aryl-, hete- Lazabemide, a monamine oxidase B in- lished in the mid-seventies by the pio- ro-aryl-, vinyl-, allyl- und benzyl-X com- hibitor. In this process the aminocar- neering work of Heck and co-workers pounds can also serve as starting materi- bonylation of the commercially available [1]. Since that time these reactions have als in these carbonylations [2]. Two ex- 2,5-dichloropyridine with ethylenedi- found a number of applications in organ- amples for carbonylation reactions of ben- amine is performed with a Pd/dppp cata- ic synthesis, and even some industrial zyl-X applied on an industrial scale for lyst with comparably high catalyst pro- processes (see below) have been realized. -
Oxidative Addition & Reductive Elimination
3/1/2021 Oxidative Addition & Reductive Elimination Robert H. Crabtree: Pages 159 – 182 and 235 - 266 1 Oxidative Addition Change in Example Group configuration • Oxidative addition is a key step in many transition-metal catalyzed reactions 10 8 I III • Basic reaction: d d Cu Cu 11 X X Pd0 PdII 10 LnM + LnM Pt0 PtII 10 Y Y d8 d6 PdII PdIV 10 • The new M-X and M-Y bonds are formed using the electron pair of the X-Y PtII PtIV 10 bond and one metal-centered lone pair IrI IrIII 9 RhI RhIII 9 • The metal goes up in oxidation state (+2), X-Y formally gets reduced to X-, Y- d6 d4 ReI ReIII 7 • The ease of addition (or elimination) can be tuned by the electronic and 0 II steric properties of the ancillary ligands Mo Mo 6 • OA favored by strongly e-donating L d4 d2 MoII MoIV 6 • The most common applications involve: a) Late transition metals (platinum metals: Ru, Rh, Pd, Ir, Pt) - not d7 d6 2CoII 2CoIII 9 too sensitive to O2 and H2O; routinely used in organic synthesis b) C-Halogen, H-H or Si-H bonds d4 d3 2CrII 2CrIII 6 • Common for transition metals, rare for main-group metals but: Grignard reagents! 2 1 3/1/2021 Oxidative addition – concerted mechanism Concerted addition - mostly with non-polar X-Y bonds X X X LnM + LnM LnM Y Y Y A Cr(CO)5: • H2, silanes, alkanes, ... coordinatively Cr(PMe3)5: • Arene C-H bonds more reactive than alkane C-H bonds unsaturated, but metal- centered lone pairs not phosphines are better • H-H, C-H strong bond, but M-H and M-C bonds can be very available donors, weaker acceptors full oxidative -
Socit Chimique De France 2014 Prize Winners
Angewandte. Angewandte News Chemie Socit Chimique de France 2014 Prize Nazario Martn (Universidad Complutense de Winners Madrid) is the winner of the Prix franco-espagnol Awarded … Miguel Cataln–Paul Sabatier. Martn was featured The Socit Chimique de France has announced its here when he was awarded the 2012 EuCheMS 2014 prize winners. We congratulate all the awar- Lectureship.[4a] Martn is on the International dees and feature our authors and referees here. Advisory Boards of Chemistry—An Asian Journal, Max Malacria (Institut de Chimie des Substan- ChemPlusChem, and ChemSusChem. His report on ces Naturelles; ICSN) is the winner of the Prix modified single-wall nanotubes was recently fea- Joseph Achille Le Bel, which is awarded to tured on the cover of Chemistry—A European recognize internationally recognized research. Mal- Journal.[4b] acria studied at the Universit Aix-Marseille III, Michael Holzinger (Universit Joseph Four- where he completed his PhD under the supervision nier, Grenoble 1; UJF) is the winner of the Prix M. Malacria of Marcel Bertrand in 1974. From 1974–1981, he jeune chercheur from the Analytical Chemistry was matre-assistant with Jacques Gore at the Division. Holzinger carried out his PhD at the Universit Claude Bernard Lyon 1 (UCBL), and Friedrich-Alexander-Universitt Erlangen-Nrn- from 1981–1983, he carried out postdoctoral berg. After postdoctoral research at the Universit research with K. Peter C. Vollhardt at the Univer- Montpellier 2 (UM2) and the Max Planck Institute sity of California, Berkeley. He returned to the for Solid-State Research, and working at Robert UCBL as matre de conferences in 1983, and was Bosch, he joined Serge Cosniers group at the UJF made professor at the Universit Pierre et Marie as a CNRS charg de recherche. -
Oxidative Addition of Polar Reagents
OXIDATIVE ADDITION OF POLAR REAGENTS Organometallic chemistry has vastly expanded the practicing organic chemist’s notion of what makes a good nucleophile or electrophile. Pre-cross-coupling, for example, using unactivated aryl halides as electrophiles was largely a pipe dream (or possible only under certain specific circumstances). Enter the oxidative addition of polarized bonds: all of a sudden, compounds like bromobenzene started looking a lot more attractive as starting materials. Cross-coupling reactionsinvolving sp2- and sp-hybridized C–X bonds beautifully complement the “classical” substitution reactions at sp3electrophilic carbons. Oxidative addition of the C–X bond is the step that kicks off the magic of these methods. In this post, we’ll explore the mechanisms and favorability trends of oxidative additions of polar reagents. The landscape of mechanistic possibilities for polarized bonds is much more rich than in the non-polar case—concerted, ionic, and radical mechanisms have all been observed. Concerted Mechanisms 2 Oxidative additions of aryl and alkenyl Csp –X bonds, where X is a halogen or sulfonate, proceed through concertedmechanisms analogous to oxidative additions of dihydrogen. Reactions of N–H and O–H bonds in amines, alcohols, and water also appear to be concerted. A π complex involving η2-coordination is an intermediate in the mechanism of insertion into aryl halides at least, and probably vinyl halides too. As two open coordination sites are necessary for concerted oxidative addition, loss of a ligand from a saturated metal complex commonly precedes the actual oxidative addition event. Concerted oxidative addition of aryl halides and sulfonates. Trends in the reactivity of alkyl and aryl (pseudo)halides toward oxidative addition are some of the most famous in organometallic chemistry. -
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..f.,5$1______ -~ survey -------) WHO WAS WHO IN KINETICS, REACTION ENGINEERING, AND CATALYSIS CAMI L. JACKSON AND JOSEPH H . HOLLES University of liyoming • Laramie, WY 82071 n the tradition of "Who was Who in Transport Phenom We have tried to include the names that are encountered ena" by Byron Bird in Chemical Engineering Education,CI J frequently in textbooks for both undergraduates and gradu Iwe have developed a similar set of microbiographies for ates (by noted authors such as Levenspiel, Hill, Fogler, and persons in the fields of kinetics, reaction engineering, and Froment and Bischoff). Again, we follow Bird's lead and do catalysis. As noted by Bird, an otherwise typical lecture not include these people simply for authoring books in these can be enlivened by presenting biographical information fields . We do, however, include-where appropriate- famous about the people whose names appear in famous equations, texts written by those scientists and engineers included for dimensionless groups, plots, approximations, and theories . other reasons. We have tried to focus on those persons who The wide variety of applications for this type of information contributed to the science of a field and not just contributed to has been demonstrated by using activity breaks to teach the a specific reaction or system (e.g., Haber and Bosch). While history of our professionl21 and as trading card rewards for contributions to specific reactions or systems are important, academic performance _l31 we elected not to include them in order to limit the scope of With the introduction and widespread acceptance ofWiki the project. Finally, we have tried to include interesting non pedia, basic biographical information on many of the early technical or non-professional information where possible to contributors to the profession of chemical engineering can be show the breadth of these individuals.