Synthetic Methods of Organometallic and Inorganic Chemistry, Volume 6, 1997 E-Book

• Herausgeber: Thieme
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 571

Veröffentlichungsjahr: 2014

Beschreibung

rovides you with a balanced compilation of carefully selected and representative examples for all classes of compounds. // The conte nt of this e-book was originally published in 1997. Designed as a benchtop tool, the series includes detailed and reliable experimental procedures for the preparation of common but imp ortant starting compounds, organized according to the periodic table. Properties of the compounds and additional references are also provided. In most cases, no strict borderline has been drawn between inorganic and organometallic compounds. Instead, the material is conveniently presented so that for every group of elements, the various aspects of the chemistry are combined. Several hundred in ternational specialists with established expertise in their respective fields have contributed, resulting in proven and reliable pre parations. In view of the enormous growth of organometallic chemistry, Synthetic Methods of Organometallic and Inorganic Chemistry p

Leseprobe

Synthetic Methods of Organometallic and Inorganic Chemistry (Herrmann/Brauer)

Edited by Wolfgang A. Herrmann

Preface to the SeriesSynthetic Methods of Organometallic and Inorganic Chemistry

It was the German chemist Ludwig Vanino1 (1861 – 1941) (▶ Figs. 1 and 3) who wrote the famous Handbuch der Präparativen Chemie (Handbook of Synthetic Chemistry). This book became well known in all chemical laboratories of the time. It contained a comprehensive collection of standard inorganic and organic laboratory procedures compiled in one volume and was originally intended to support practical courses in Adolf von Baeyer’s laboratory in Munich (▶ Fig. 3). When the third edition of the “Vanino” went out of print in the year of 1940, the Ferdinand Enke publishing company (Stuttgart, Germany) developed a new concept in which procedures for the preparation of scientifically interesting and didactically important inorganic compounds were compiled. The main emphasis was placed on the reliability and reproducibility of the reported procedures.

1Ber. dtsch. chem. Ges.74, A232 (1941); Chem.-Ztg.65, 402 (1941).

▶ Figure 1Ludwig Vanino, the editor of the “Handbuch der Präparativen Chemie”. After receiving his doctor’s degree at the University of Erlangen in 1891, Vanino became a co-worker of Hans von Pechmann (Munich) and was later (1911) awarded the title of a “Königlicher Professor” (Bavarian Royal Professor).

▶ Figure 2 Professor Georg Brauer (1908 –), the founder of the “Handbuch der Präparativen Anorganischen Chemie” bearing his name since 1954.

▶ Figure 3 The “Anorganische Abteilung” of the Munich chemistry laboratory under the direction of Adolf von Baeyer (front row, middle) during the summer semester of 1898. Ludwig Vanino is in the second row (third from the left).

As a result of World War II, the first edition of the new Handbuch der Präparativen Anorganischen Chemie did not appear until 1954. Georg Brauer (1908 –) (▶ Fig. 2), a professor of inorganic chemistry at the University of Freiburg (Germany), merits respect not only for having started the new “Handbuch” in difficult times but also for creating a standard book of chemical recipes which became famous throughout the world in spite of being published in German. The third edition, meanwhile expanded to three volumes, was completed in 1981. On that occasion, organometallic compounds were included for the first time as a separate chapter (W. P. Fehlhammer, W. A. Herrmann, K. Öfele: Metallorganische Komplexverbindungen) in the third volume to cope with the enormous growth experienced by this class of compounds in the years following publication of the first edition, as exemplified by two milestones, the discovery of ferrocene in 1951/19522 and dibenzenechromium in 19553.

2 (a) T. J. Kealey, P. L. Pauson, Nature168, 1039 (1951).(b) S. A. Miller, J. A. Tebboth, J. F. Tremaine, J. Chem. Soc. (London) 632 (1952).

3 E. O. Fischer, W. Hafner, Z. Naturforsch.10b, 665 (1955).

The special and wide-ranging influence of organometallic chemistry upon chemical science in general and the necessity for the worthy successor to Vanino and Brauer has required a new conception as well as the publication of “Synthetic Methods of Organometallic and Inorganic Chemistry” in English. A total of eight volumes are planned to cover the most important standard compounds that appear to be in general use in laboratories engaged in all branches of synthetic chemistry. In most cases, no strict borderline has been drawn between inorganic and organometallic compounds. Instead, we have attempted to keep up with the developments in coordination and organometallic chemistry, areas which were underrepresented in the previous first (1954), second (1960), and third (1975 – 1981) editions of Brauer. The material is presented in such a way that, for every group of elements, the various aspects of the chemistry are combined. The following volumes are planned for the series (the names of the volume editors are given in parentheses):

Volume 1

Literature, Laboratory Techniques, and Common Starting Materials (

W. A. Herrmann/A. Salzer

)

Volume 2

Groups 1, 2, 13, and 14 (

N. Auner/U. Klingebiel

)

Volume 3

Phosphorus, Arsenic, Antimony, and Bismuth (

H. H. Karsch

)

Volume 4

Sulfur, Selenium, and Tellurium (

K. J. Irgolic/N.N.

)

Volume 5

Copper, Silver, Gold, Zinc, Cadmium, and Mercury (

D. Breitinger/W. A. Herrmann/W. Hiller

)

Volume 6

Lanthanides and Actinides (

F. Edelmann

)

Volume 7

Transition Metals, Part 1 (

W. A. Herrmann/F. R. KreißI

)

Volume 8

Transition Metals, Part 2 (

W. A. Herrmann/F. R. Kreißl

)

In view of the enormous growth of organometallic chemistry, particularly in the past 20 years, the editors were faced with the difficult task of selecting typical compounds in general use and thus no claims of a comprehensive and complete coverage can be made. However, the user of this recipe book may expect– and will hopefully find – a balanced selection of older and newer examples of all classes of compounds with detailed and reliable experimental procedures in the eight volumes of this series. Separated from each other since the days of Ludwig Vanino, organic aspects have once again been integrated into inorganic chemistry.

The series editor gratefully acknowledges the help of numerous colleagues who have acted as volume editors and donated their expertise in their respective fields or who have contributed well-proven preparations. It must be emphasized, however, that neither the editors nor the contributors can undertake any liability for problems resulting from any of the given procedures. It is the responsibility of every laboratory worker to take all precautions necessary to ensure his/her safety and the safety of all others in the vicinity.

The editor is also indebted to Dr. Joe P. Richmond of Georg Thieme Verlag and Dr. Richard Dunmur, the desk editor, for their patient and competent help in the preparation of this balanced and well-organized new handbook series. Furthermore, the technical assistance of Dr. Florian Dyckhoff and Mr. Thomas Dambacher is much appreciated.

Garching, November 1995

Wolfgang A. Herrmann

Technische Universität München

Preface to Volume 6

The lanthanide and actinide elements are sometimes termed the “footnotes of the Periodic Table” and, in fact, even to many chemists these elements appear somewhat obscure and their chemistry difficult to rationalize. However, especially the elements of the lanthanide series are of great industrial and technological importance. Their various uses range from novel catalysts to “high tech” materials and versatile reagents in organic synthesis. The beginning of organo lanthanide and organoactinide chemistry dates back to the years 1954 and 1956, respectively. In both areas the early discoveries were followed by periods of relative stagnation, as it turned out that most organo-f-element compounds were highly air sensitive and not easily characterized. The past 15 years have witnessed an exciting development of this particular area of organometallic chemistry. During this time organolanthanide and actinide compounds have turned from “laboratory curiosities” to highly useful materials. Not only do these compounds often exhibit unusual molecular structures which have no parallel in the organometallic chemistry of the d-transition metals but it is also the often unprecedented reactivity and unusually high catalytic activity which makes many of these compounds truly unique. Provided the proper choice of ancillary ligands (e.g., pentamethylcyclopentadienyl), highly reactive though thermally stable organolanthanide and -actinide hydrocarbyls and hydrides have now become readily accessible. With today’s more sophisticated synthetic techniques and spectroscopic methods these compounds are easily isolated and fully characterized. X-ray diffraction studies have contributed a great deal to the understanding of the structural chemistry of organo-f-element compounds.

The present Volume 6 of “Synthetic Methods of Organometallic and Inorganic Chemistry” contains procedures for inorganic compounds of the lanthanides and actinides as well as a number of important starting materials. The main emphasis however, has been placed on the various types of organo-f-element complexes. In these sections the author has tried to make a reprepresentative selection covering all important aspects of the field. Naturally such a selection is partially influenced by the author’s special interests but all efforts have been made to be as comprehensive as possible. Special attention has been paid to important precursor materials. A few examples of transuranium organometallics have been included in this volume despite the fact that only a few laboratories in the world are properly equipped to handle these materials. The intention was to demonstrate that certain organometallic compounds are accessible even for these elements.

The author wishes all users of “Synthetic Methods of Organometallic and Inorganic Chemistry” good success with the preparations described in this volume. With respect to future editions of this handbook any comments and criticism from colleagues are most welcome.

Magdeburg, July 1996

Frank T. Edelmann

Contents

Chapter 1Inorganic Compounds and Important Starting Materials of the Lanthanide Elements

Frank T. Edelmann and Peter Poremba

1.1 Introduction

1.2 Inorganic Compounds

1.3 Important Starting Materials

1.3.1 Lanthanide(II) Derivatives

1.3.2 Lanthanide(III) Derivatives

1.3.3 Lanthanide(IV) Derivatives

Chapter 2Organolanthanide Compounds

Frank T. Edelmann and Peter Poremba

2.1 Introduction

2.2 Organolanthanide(0) Complexes

2.3 Organolanthanide(II) Complexes

2.4 Organolanthanide(III) Complexes

2.5 Organolanthanide(IV) Complexes

Chapter 3The Actinide Elements and Their Inorganic Compounds

Frank T. Edelmann and Peter Poremba

3.1 Introduction

3.2 Thorium and its Inorganic Compounds

3.3 Uranium and its Inorganic Compounds

3.4 Neptunium and its Inorganic Compounds

Chapter 4Organoactinide Complexes

Frank T. Edelmann and Peter Poremba

4.1 Introduction

4.2 Actinide(IV) Compounds with Cyclopentadienyl Ligands

4.2.1 Tetrakis(cyclopentadienyl)actinides(IV)

4.2.2 Tris(cyclopentadienyl)actinide(IV) Complexes

4.2.3 Bis(cyclopentadienyl)actinide(IV) Complexes

4.2.4 Mono(cyclopentadienyl)actinide(IV) Complexes

4.3 Organoactinides(IV) without Cyclopentadienyl Ligands

4.4 Cyclooctatetraenyiactinide(IV) Compounds

4.5 Compounds with Element-Actinide Multiple Bonds

4.6 Actinide(III) Compounds

Index

Chapter 1 Inorganic Compounds and Important Starting Materials of the Lanthanide Elements

Frank T. Edelmanna and Peter Porembab

a Chemisches Institut der Otto-von-Guericke-Universität, Universitätsplatz 2, D-39106 Magdeburg, Germany

b Institut für Anorganische Chemie der Universität Göttingen, Tammannstraße 4, D-37077 Göttingen, Germany

With contributions from:Anwander, R., GarchingAtwood, J. L., ColumbiaBradley, D. C., LondonCaro, P. E., Meudon-BellevueCloke, F. G. N., BrightonDeacon, G. B., ClaytonDeming, T. J., IrvineDrummond, D. K., IrvineEdelmann, F. T., MagdeburgEvans, W. J., IrvineFeng, T., ClaytonFischer, R. D., HamburgFreeman, J. H., HarwellGhotra, J. S., LondonGirard, P., OrsayHahn, F. E., BerlinHart, F. A., LondonHerrmann, W. A., GarchingHitchcock, P. B., BrightonHolmes, S. A., BrightonKagan, H. B., OrsayKleine, M., GarchingLaDuca, R. L., IthacaLappert, M. F., BrightonMacKinnon, P., ClaytonMohr, J., BerlinNamy, J. L., OrsayNewnham, R. H., ClaytonNickel, S., ClaytonNoltemeyer, M., GöttingenOlofson, J. M., IrvinePieper, U., GöttingenScherer, W., GarchingSchmidt, H.-G., GöttingenSen, A., University ParkSingh, A., BrightonSkelton, B. W., NedlandsSmith, M. L., HarwellSmith, R. G., BrightonStalke, D., GöttingenStecher, H. A., University ParkSteudel, A,. HamburgTulip, T. H., WilmingtonTuong, T. D., ClaytonWatson, P. L., WilmingtonWedler, M., GöttingenWhite, A. H., NedlandsWilkinson, D. L., ClaytonWilliams, I., WilmingtonWolczanski, P. T., IthacaZhang, H., IrvineZiller, J. W., Irvine

1.1 Introduction

1.2 Inorganic Compounds

1.3 Important Starting Materials

1.3.1 Lanthanide(II) Derivatives

1.3.2 Lanthanide(III) Derivatives

1.3.3 Lanthanide(lV) Derivatives

1.1 Introduction

The lanthanide (rare earth) elements or lanthanoids are lanthanum (La), cerium (Ce), praesodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). In some cases related scandium (Sc) and yttrium (Y) compounds are also discussed. In general equations in the following text, the “element symbol” Ln will be used whenever necessary.

1.2 Inorganic Compounds

The procedures reported in this section have been selected and translated from Chapter 20 by G. Brauer, in G. Brauer (ed.), Handbuch der Präparativen Anorganischen Chemie, Vol. 2, pp. 1066 – 1116, Ferdinand Enke Verlag, Stuttgart, 1978. A more recent review on inorganic lanthanide compounds has been published: G. Meyer, L. R. Morss (eds.), Synthesis of Lanthanide and Actinide Compounds, Kluwer, Dordrecht, Boston, London, 1991.

Rare Earth Metal(III) Chlorides, Bromides, Iodides1,2 — LnX3

Preparation of Chlorides

Method A:3,4 The dehydration of LnCl3 · n H2O to the pure anhydrous trichloride can be achieved with the help of NH4Cl since the latter counteracts hydrolysis:

LnCl3 · H2O + m NH4Cl → LnCl3 + m NH3 + m HCl + n H2O

The salt LnCl3 · n H2O (1 equiv.) is powdered as finely as possible and well mixed with 4 – 6 equivalents of NH4Cl. The mixture can also be produced by evaporating a solution of the two compounds to dryness. The solid mixture is filled into a vertically or horizontally positioned tube made of Pyrex or quartz glass and closed at one end. When high purity is needed, the reaction mixture can be placed in a molybdenum boat to exclude reaction with the glass wall:

2 LnCl3 + SiO2 → 2 LnOCl + SiCl4

As shown in ▶Figure 1.1 A or B, the reaction site a is separated from a further section of tube b to receive the sublimed material by a narrowed section.

Tube a is heated by an electric tube oven o; tube b is joined with a high vacuum system via a cooled trap c and with a fitting d for the supply of an inert, well-dried gas (e.g., N2). The reaction tube a with contents is heated very slowly and a high vacuum (approx. 10−2 torr) is maintained therein dynamically. Especially in the initial stage, when the temperature is raised from 20 to 100 °C and most of the water is expelled, attention must be paid to the quality of the vacuum. After some time, the temperature can be raised slowly to approx. 400 °C to sublime off NH4Cl completely from LnCl3. Water and NH4Cl accumulate in tube b and trap d. The time program for the temperature increase is aimed at the continuous maintenance of a good vacuum and depends on the respective rare earth metal and the amount of substance to be processed; it can range from a few hours to days. LaCl3 · n H2O can be dehydrated rapidly; the duration of the dehydration must be extended with the decreasing basicity of the metal. Excessively rapid heating not only increases the danger of hydrolysis but also decreases the yield because some trichloride is carried away mechanically by the subliming NH4Cl.