ATOMIC WEIGHTS OF THE ELEMENTS a, b (adapted from T.B. Coplen et al., Inorg. Chim. Acta 217, 217, 1994) Element Symbol Atomic Atomic Element Symbol Atomic Atomic Number Weight Number Weight Actiniumc 227Ac 89 227.03 Mercury Hg 80 200.59(2) Aluminum Al 13 26.982 Molybdenum Mo 42 95.94 Americiumc Am 95 241.06 Neodynium Nd 60 144.24(3) Antimony Sb 51 121.76 Neon Ne 10 20.180 Argon Ar 18 39.948 Neptuniumc 237Np 93 237.05 Arsenic As 33 74.922 Nickel Ni 28 58.693 Astatinec 210At 85 209.99 Niobium Nb 41 92.906 Barium Ba 56 137.33 Nitrogen N 7 14.007 Berkeliumc 249Bk 97 249.08 Nobeliumc 259No 102 259.10 Beryllium Be 4 9.0122 Osmium Os 76 190.23(3) Bismuth Bi 83 208.98 Oxygen O 8 15.999 Boron B 5 10.811(5) Palladium Pd 46 106.42 Bromine Br 35 79.904 Phosphorus P 15 30.974 Cadmium Cd 48 112.41 Platinum Pt 78 195.08(3) Calcium Ca 20 40.078(4) Plutoniumc 239Pu 94 239.05 Californiumc 232Cf 98 252.08 Poloniumc 210Po 84 209.98 Carbon C 6 12.011 Potassium K 19 39.098 Cerium Ce 58 140.12 Praseodynium Pr 59 140.91 Cesium Cs 55 132.91 Promethiumc 147Pm 61 146.92 Chlorine Cl 17 35.453 Proactiniumc Pa 91 231.04 Chromium Cr 24 51.996 Radiumc 226Ra 88 226.03 Cobalt Co 27 58.933 Radonc 222Rn 86 222.02 Copper Cu 29 63.546(3) Rhenium Re 75 186.21 Curiumc 244Cm 96 244.06 Rhodium Rh 45 102.91 Dysprosiumc Dy 66 162.50(3) Rubidium Rb 37 85.468 Einsteiniumc 252Es 99 252.08 Ruthenium Ru 44 101.07(2) Erbium Er 68 167.26(3) Samarium Sm 62 150.36(3) Europium Eu 63 151.96 Scandium Sc 21 44.956 Fermiumc 257Fm 100 257.1 Selenium Se 34 78.96(3) Fluorine F 9 18.998 Silicon Si 14 28.086 Franciumc 223Fr 87 223.02 Silver Ag 47 107.87 Gadolinium Gd 64 157.25(3) Sodium Na 11 22.990 Gallium Ga 31 69.723 Strontium Sr 38 87.62 Germanium Ge 32 72.61(2) Sulfur S 16 32.066(6) Gold Au 79 196.97 Tantalum Ta 73 180.95 Hafnium Hf 72 178.49(2) Technetiumc 99Tc 43 98.906 Helium He 2 4.0026 Tellurium Te 52 127.60(3) Holmium Ho 67 164.93 Terbium Tb 65 158.93 Hydrogen H 1 1.0079 Thallium Tl 81 204.38 Indium In 49 114.82 Thoriumc Th 90 232.04 Iodine I 53 126.9 Thulium Tm 69 168.93 Iridium Ir 77 192.22 Tin Sn 50 118.71 Iron Fe 26 55.845(2) Titanium Ti 22 47.867 Krypton Kr 36 83.8 Tunsgten W 74 183.84 Lanthanum La 57 138.91 Uraniumc U 92 238.03 Lawrenciumc 262Lw 103 262.11 Vanadium V 23 50.942 Lead Pb 82 207.02 Xenon Xe 54 131.29(2) Lithium Li 3 [6.941(2)]b Ytterbium Yb 70 173.04(3) Luteciumc Lu 71 174.97 Yttrium Y 39 88.906 Magnesium Mg 12 24.305 Zinc Zn 30 65.39(2) Manganese Mn 25 54.938 Zirconium Zr 40 91.224(2) Mendeleviumc 258Mv 101 258.1 a : based on a mass for 12C of 12.000. b : given five significant digits; if less, the errors are given in parentheses after the atomic mass. c : indicates the most known isotope for artificial elements. Didier Astruc Organometallic Chemistry and Catalysis Grenoble Sciences Grenoble Sciences pursues a triple aim: • to publish works responding to a clearly defined project, with no curriculum or vogue constraints, • to guarantee the selected titles’ scientific and pedagogical qualities, • to propose books at an affordable price to the widest scope of readers. Each project is selected with the help of anonymous referees, followed by an average one-year interaction between the authors and a Readership Committee whose members’ names figure in the front pages of the book. Grenoble Sciences then signs a co-publishing agreement with the most adequate publisher. (Contact: T´el.: (33) (0)4 76 51 46 95 – Fax: (33) (0)4 76 51 45 79 – E-mail: [email protected]) Scientific Director of Grenoble Sciences: Jean Bornarel, Professor at the Joseph Fourier Univer- sity, France Grenoble Sciences is supported by the French Ministry of Education and Research and the “R´egion Rhone-Alpes”.ˆ “Organometallic Chemistry and Catalysis” is an improved version of the French book published by Grenoble Sciences in partnership with EDP Sciences. The Reading Committee of the French version included the following members: Yves Chauvin, Nobel prizewinner (2005), Honorary Scientific Director of the French Petrol Institute, Robert Corriu, Member of the French Academy of Science and the French University Institute, professor at the University of Montpellier, Jean-Ren´e Hamon, Senior Researcher at the CNRS, University of Rennes Henri Kagan, Member of the French Academy of Science and the French University Institute, professor at he University of Paris-Sud, Orsay, Paul Knochel, Professor at the Ludwig Maximilians Universit¨at, Munchen,¨ Bernard Meunier, Member of the French Academy of Science, Senior researcher at the CNRS in Toulouse, Jean-Franc¸ois Normant, Member of the French Academy of Science, professor at the Pierre et Marie Curie University, Paris Jean-Yves Saillard, professor at the University of Rennes Jean-Pierre Sauvage, Member of the French Academy of Science, Senior researcher at the CNRS in Strasbourg, Bernard Waegell, professor at the University of Aix-Marseille Didier Astruc Organometallic Chemistry and Catalysis With 860 Figures and 27 Tables 123 Didier Astruc Member of the Institut Universitaire de France Institut des Sciences Mol´eculaires, Groupe Nanosciences Mol´eculaires et Catalyse UMR CNRS N◦ 5255 Universit´eBordeauxI 351, Cours de la Lib´eration 33405 Talence Cedex France email: [email protected] Originally published in French: Didier Astruc, Chimie Organom´etallique, EDP Sciences, Grenoble 2000, ISBN 978-2-86883-493-5 Library of Congress Control Number: 2007924912 ISBN 978-3-540-46128-9 Springer Berlin Heidelberg New York DOI 10.1007/978-3-540-46129-6 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable forprosecutionundertheGermanCopyrightLaw. Springer is a part of Springer Science+Business Media springer.com © Springer-Verlag Berlin Heidelberg 2007 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Camera ready by Grenoble Sciences Production: LE-TEXJelonek,Schmidt&VöcklerGbR,Leipzig Cover Design: Nicole Sauval, Grenoble, France Front Cover Illustration: composed by Alice Giraud with extracts from E.Alonso,D.Astruc–IntroductionoftheClusterFragmentRu3(CO)11 at the periphery of Phosphine Dendrimers Catalyzed by the Electron-Reservoir Complex [FeI Cp(C6Me6)], J. Am. Chem. Soc. 2000, 122, 3222 Printed on acid-free paper 2/3180/YL 5 4 3 2 1 0 PREFACE This text is a translation and thorough revision of the French book “Chimie Organométallique” that was published by EDP Sciences in 2000 and whose Spanish version, prepared by Carmen Claver and Beatriz Alonso, was published by Reverte in 2003. The catalysis part has been considerably extended, however. Not only has it been re-organized and complemented, but new chapters have been written on homogeneous catalytic hydrocarbon activation and on heterogeneous catalysis. I would like to thank the colleagues who have corrected parts of the French Edition: Yves Chauvin (IFP and Villeurbanne) for the catalysis section, Jean-René Hamon (Rennes) who read the entire French version, Catherine Hemmert (LCC, Toulouse), who corrected the enzymatic catalysis chapter, Henri Kagan (Orsay) for general advice, Jean-Yves Saillard (Rennes) for the theoretical aspects and Bernard Waegel (Marseille) for remarks on the catalysis chapters. I am grateful to Alan H. Cowley (U.T. Austin), Andrew Wojcicki (Columbus), Jonathan Egbert and Travis J. Ebden (Seattle) for proofreading several chapters of the English text and to Cátia Ornelas (Talence) for proofreading the entire book. Finally, it is a great pleasure to thank Jean Bornarel and Nicole Sauval for their editorial efforts as well as Sylvie Bordage (Grenoble Sciences) for her superb work in the book production and Theodor C.H. Cole (Springer) for excellent copy-editing. Didier ASTRUC, Talence, February 2007 CONTENTS Introduction.......................................................................................................... 1 1. Organization of the text...................................................................................... 1 2. Frontiers of organometallic chemistry................................................................ 2 3. Situation of the book with respect to teaching .................................................... 2 4. Reference books and other selected references................................................... 3 History of organometallic chemistry ................................................................... 5 1760-1900:The first complexes.............................................................................. 5 1900-1950:Grignard, Sabatier, and catalysis in Germany ....................................... 6 1950-1960:The discovery of ferrocene and the boom of organometallic chemistry. 7 1961-1981:The discovery of multiple metal-carbon bonds and the golden age of catalysis ............................................................. 9 1970-1985:Activation of C-H bonds in hydrocarbons, -bond metathesis and H2 as a ligand................................................. 16 Current trends....................................................................................................... 18 PART I STRUCTURES OF THE TRANSITION-METAL COMPLEXES Chapter 1 - Monometallic transition-metal complexes..................................... 23 1.