Gmelin Handbook of Inorganic Chemistry

8th Edition Organametallic Compounds in the Gmelin Handbook

The following listing indicates in which volumes these compounds are discussed or are referred to:

Ag Silber B 5 (1975)

Au Organogold Compounds (1980)

Bi Bismut-Organische Verbindungen (1977)

Co Kobalt-Organische Verbindungen 1 (1973), 2 (1973), Kobalt Erg.-Bd. A (1961), B 1 (1963), B 2 (1964)

Cr Chrom-Organische Verbindungen (1971)

Cu Organacopper Compounds 1 (1985), 2 (1983)

Fe Eisen-Organische Verbindungen A 1 (1974), A 2 (1977), A 3 (1978), A 4 (1980), A 5 (1981 ), A 6 (1977), A 7 (1980), Organoiron Compounds A 8 (1986) present volume, Eisen-Organische Verbindungen B 1 (partly in English; 1976), B 2 (1978), B 3 (partly in English; 1979), B 4 (1978), B 5 (1978), Organoiron Compounds B 6 (1981 ), B 7 (1981 ), B 8 to B 10 (1985), B 11 (1983), B 12 (1984), Eisen-Organische Verbin• dungen C 1 (1979), C 2 (1979), Organoiron Compounds C 3 (1980), C 4 (1981), C 5 (1981), C 7 (1986), and Eisen B (1929-1932)

Hf Organahafnium Compounds (1973)

Nb Niob B 4 (1973)

Ni Nickel-Organische Verbindungen 1 (1975), 2 (1974), Register (1975), Nickel B 3 (1966), and C 1 (1968), C 2 (1969)

Np, Pu Transurane C (partly in English; 1972)

Pt Platin C (1939) and D (1957)

Ru Ruthenium Erg.-Bd. (1970)

Sb Organoantimony Compounds 1 (1981), 2 (1981), 3 (1982)

Sc, Y, 0 6 (1983) La to Lu

Sn Zinn-Organische Verbindungen 1 (1975), 2 (1975), 3 (1976), 4 (1976), 5 (1978), 6 (1979), Organotin Compounds 7 (1980), 8 (1981), 9 (1982), 10 (1983), 11 (1984), 12 (1985)

Ta Tantal B 2 (1971)

Ti Titan-Organische Verbindungen 1 (1977), 2 (1980), 3 (1984), 4 and Register (1984)

U Uranium Suppt. Vol. E 2 (1980)

V Vanadium-Organische Verbindungen (1971), Vanadium B (1967)

Zr Organozirconium Compounds (1973) Gmelin Handbook of lnorganic Chemistry

8th Edition

Gmelin Handbuch der Anorganischen Chemie

Achte, völlig neu bearbeitete Auflage

Prepared Gmelin-lnstitut für Anorganische Chemie and issued by der Max-Planck-Gesellschaft zur Förderung der Wissenschaften Director: Ekkehard Fluck

Founded by Leopold Gmelin 8th Edition 8th Edition begun under the auspices of the Deutsche Chemische Gesellschaft by R. J. Meyer Continued by E. H. E. Pietsch and A. Kotowski, and by Margot Becke-Goehring

Springer-Verlag Berlin Heidelberg GmbH 1986 Gmelin-lnstitut für Anorganische Chemie der Max-Planck-Gesellschaft zur Förderung der Wissenschaften

ADVISORY BOARD Dr. J. Schaafhausen, Chairman (Hoechst AG, Frankfurt/Main-Höchst), Dr. G. Breil (Ruhr• chemie AG, Oberhausen-Holten), Dr. G. Broja (Bayer AG, Leverkusen), Prof. Dr. G. Fritz (Universität Karlsruhe), Prof. Dr. N. N. Greenwood (University of Leads), Prof. Dr. R. Hoppe (Universität Gießen), Dr. H. Moell (BASF-Aktiengesellschaft, Ludwigshafen), Prof. Dr. H. Nöth (Universität München), Prof. Dr. G. zu Putlitz (Universität Heidelberg), Prof. Dr. A. Rabenau (Max-Planck-lnstitut für Festkörperforschung, Stuttgart), Prof. Dr. Dr. H. A. Staab (Präsident der Max-Planck-Gesellschaft, München), Prof. Dr. Dr. h. c. mult. G. Wilke (Max-Planck-lnstitut für Kohlenforschung, Mülheim/Ruhr)

DIRECTOR DEPUTY DIRECTOR Prof. Dr. Dr. h. c. Ekkehard Fluck Dr. W. Lippert

CHIEF EDITORS Dr. K.-C. Buschback - Dr. H. Bergmann, F. Füssel, Dr. H. Katscher, Dr. R. Keim, Dipl.-Phys. D. Koschel, Dr. U. Krüerke, Dr. H. K. Kugler, Dr. P. Marlet, Dr. E. Schleitzer-Rust, Dr. A. Slawisch, Dr. F. Schröder, Dr. B. v. Tschirschnitz-Geibler, Dr. R. Warncke

STAFF D. Barthel, Dr. N. Baumann, Dr. W. Behrendt, Dr. L. Berg, Dipl.-Chem. E. Best, Dipl.-lng. V. A. Chavizon, E. Cloos, Dipl.-Phys. G. Czack, I. Deim, Dipl.-Chem. H. Demmer, R. Dowideit, Dipl.• Chem. M. Drößmar, M. Engels, Dr. H.-J. Fachmann, Dr. J. Faust, Dr. W.-D. Fleischmann, V. Frick, Dr. R. Froböse, G. Funk, Dipl.-lng. N. Gagel, E. Gerhardt, Dr. U. W. Gerwarth, M.-L. Gerwien, Dipl.-Phys. D. Gras, C. Gorr, H. Hartwig, Dipl.-Min. H. Hein, G. Heinrich-Sterzel, H.-P. Hente, H. W. Herold, U. Hettwer, Dr. I. Hinz, Dr. W. Hoffmann, Dipl.-Chem. K. Holzapfel, Dr. S. Jäger, Dr. J. von Jouanne, H.-G. Karrenberg, Dipl.-Phys. H. Keller-Rudek, Dr. L. Kießling, Dipl.-Phys. E. Koch, Dr. E. Koch, Dipl.-Chem. K. Koeber, Dipl.-Chem. H. Köttelwesch, R. Kolb, E. Kranz, Dipl.-Chem. I. Kreuzbichler, Dr. A. Kubny, Dr. P. Kuhn, Dr. W. Kurtz, M. Langer, Dr. A. Leonard, Dipl.-Chem. H. List, H. Mathis, E. Meinhard, Dr. M. Mirbach, Dr. U. Neu-Becker, K. Nöring, Dipl.-Chem. R. Nohl, Dipl.-Min. U. Nohl, Dr. W. Petz, I. Rangnow, Dipl.-Phys. H.-J. Richter-Ditten, Dipl.-Chem. H. Rieger, B. Riegert, E. Rieth, A. Rosenberger, Dr. B. Roth, E. Ru• dolph, G. Rudolph, Dipl.-Chem. S. Ruprecht, Dr. R. C. Sangster, V. Schlicht, Dipl.-Chem. D. Schneider, Dipl.-Min. P. Schubert, A. Schwärzet, Dipl.-lng. H. M. Somer, E. Sommer, M. Teichmann, Dr. W. Töpper, Dipl.-lng. H. Vanecek, Dipl.-Chem. P. Velic, Dipl.-lng. U. Vetter, H.-M. Wagner, Dipl.-Phys. J. Wagner, R. Wagner, Dr. E. Warkentin, Dr. B. Wöbke, K. Wolff, U. Ziegler

CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF Dr. J. R. Clark, Dr. D. B. Gerth, Dr. J. L. Grant, Dr. K. Rumpf, Dr. K. Swars, Dr. U. Trobisch, Dr. B. Vance

EMERITUS MEMBER OF THE INSTITUTE Prof. Dr. Dr. E. h. Margot Backe

CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Hans Bock Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.) Gmelin Handbook of lnorganic Chemistry

8th Edition

Fe Organoiron Compounds

Part A Ferrocene 8

Mononuclear Disubstituted Ferrocene Derivatives with C-, H-, and 0-Containing Substituents (continued from "Ferrocene" 7)

With 14 illustrations

AUTHOR Marianne Drößmar-Wolf

EDITOR Adolf Slawisch

FORMULA INDEX Edgar Rudolph

CHIEF EDITOR Adolf Slawisch

Springer-Verlag Berlin Heidelberg GmbH 1986 LlTERATURE CLOSING DATE: 1984 IN SOME CASES MORE RECENT DATA HAVE BEEN CONSIDERED

Library of Congress Catalog Card Number: Agr 25-1383

ISBN 978-3-662-08852-4 ISBN 978-3-662-08850-0 (eBook) DOI 10.1007/978-3-662-08850-0

This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, reuse of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under § 54 of the German Copyright Law where copies are made for other than private use, a fee is payable to "Verwertungsgesellschatt Wort", Munich.

The use of registered names, trademarks, etc., In this publicatian does not imply, even in the absence of a specific slatement, that such names are exempt from the relevant protective laws and regulatiQns and therefore free for general usa. Preface

"Organoiron Compounds" A, Ferrocene 8 systematically covers the Literature through the end of 1984 and even includes some references published more recently. A formula index for the volumes "Organoiron Compounds" A, Ferrocene 7 and 8 provides ready access to the compounds covered.

This volume continues the description of ferrocenes FeC10H8R1R2 in which at least R1 contains C, H, and 0. The description of these type of compounds started in "Organoiron Compounds" A, Ferrocene 7 (with alcohols and phenols, their esters, ethers and acetones, and aldehydes). Series Aso far comprises volumes A 1 to A 8, and it has been surveyed in the preface to A 7 (1980). The data in tables are given in abbreviated form without dimensions; for dimensions, explanations, and further abbreviations used, see p. VIII (next page). Additional remarks, if necessary, are given in the headings of the tables.

Frankfurt Adolf Slawisch November 1985 VIII

Remarks on Abbreviations and Dimensions Many compounds in this volume are presented in tables in which numerous abbreviations are used, and the dimensions are omitted for the sake of conciseness. This necessitates the following clarification:

Temperstures are given in oc, otherwise K stands for Kelvin. Abbreviations used with temperatures are m.p. for melting point, b.p. for boiling point, dec. for decomposition, and sub!. for sublimation. The solvent in parentheses following the m.p. is the solvent from which the compound is recrystallized.

NMR represents nuclear magnetic resonance. Chemical shifts are given as ö values in ppm; reference substances and signs for ö are shown in the scheme below:

increasing field ~

ö=O for 1H + Si(CH3)4 11ß + BF3 · O(C2Hsl2 Coupling constants in Hz are given as "J (A, 8) 13C and + Si(CH3)4 refer to Labelied structural formulas, n is number of bonds between the coupled nuclei. 19f CFCL3 + 31p + H3P04

Multiplicities of the signals are abbreviated as s, d, t, q (singlet to quartet), quint, sext, sept, oct (quintet to octet), and m (multiplet); terms like dd (double doublet) and dq (double quartet) arealso used. Assignments referring to Labelied structural formulas are given in the form C-4, H-3,5.

For Mössbauer spectra both the isomer shift ö and the quadrupole splitting ß are given in mm/s; the reference substances for ö are indicated after the numerical value, e.g. ö = 0.31 (57Co/Cu).

Optical spectra are Labelied as IR (infrared) and UV (electronic spectrum including the visible region): IR bands are given in cm-1; the assigned bands are usually Labelied with the symbols v for Stretching vibration and ö and y for deformation Vibrations in-plane and out-of• plane, respectively. The indices "s" and "a" mean symmetrical and asymmetrical. lntensities occur in parentheses in the common qualitative terms (s, m, w, vs, br., etc.). The UV absorption maxima, Amax• are given in nm followed bythe extinction coefficient e(L·cm-1· mol-1) orlogEin parentheses; sh means shoulder.

Solvents used and the temperatures (in oc or K) are given in parentheses immediately atter the spectral symbol. Common solvents are given by their formula or name except THF and DMF, which represents tetrahydrofuran and (CH3hNCHO, respectively. For solvent mixtures are given volume ratios.

For the mass spectrum a parenthetical (Cl) means chemical ionization. ln all other cases the ions are generated by electron impact. [M]+ denotes the molecular ion.

Further abbreviations used are nb for refractive index for the sodium line, 589 nm, at t in oc; [alt and [MJl for specific and molar rotation for light of wavelength 1.. in nm at t in oc; c for concentration, when no unit is stated either g/L or grams per 100 mL can be assumed; mol. wt for molecular weight; (meas.) for measured and (calc.) for calculated values; ESR for electron spin resonance; hfs for hyperfine structure. IX

Table of Contents

Mononuclear Disubstituted Ferrocene Derivatives with C-, H·, and 0-Containing Substituent&

Page Remarks on Abbreviation& and Dimensions ...... VIII

5.2.3.5 Ketones ...... 2

5.2.3.5.1 1,1 '-Compounds ...... 2

1,1 '-Diacetylferrocene Fe{C5H4-GO-CH3h ...... 2 Formation and Preparation ...... 2 Purification ...... 4 Separation ...... 4 Analysis ...... 5 Physical and Structural Properties ...... 7 Thermal Properties ...... 7 Dipole Moment ...... 8 Molar Refraction ...... 8 Nuclear Resonance Spectra ...... 8 57 Fe Mössbauer Spectrum ...... 9 IR and Raman Spectra ...... 13 Electronic Absorption Spectra ...... 15 Magnetic Circular Dichroism ...... 15 Photoelectron Spectrum ...... 15 Crystal Structure ...... 15 Molecular Structure ...... 15 Solubility ...... 20 Electrochemical Behavior ...... 21 Chemical Behavior ...... 23 Reactions with Cleavage of the Iron-Cyclopentadienyl Bond ...... 23 Thermal Decomposition ...... 23 Mass Spectrum ...... 23 Photochemical Reactions ...... 24 Other Decomposition Reactions ...... 24 Oxidation ...... 26 To the Ferrocenium Ion ...... 26 To Fe{C5H4-CO-GH20Hh and Fe{C5H4-CO-CH0h ...... 27 To Fe{C5H4-G02Hh and H02C-G5H4FeC5H4-CO-GH3 ...... 27 Reduction ...... 28 Substitution Reactions on the Cyclopentadienyl Rings ...... 30 Basicity and Complex Formation ...... 31 Basicity ...... 31 Complex Formation ...... 31 Reactions on the Substituents ...... 33 Nucleophilic Addition to the CO Group ...... 33 Of N-Containing Nucleophiles ...... 33 Of Organometallic Compounds ...... 36 Of Other Nucleophiles ...... 37

Gmelin Handbock Fe-Org. Comp. A 8 X

Page

Behavior of the CH 3CO Groups as CH Acid Components ...... 38 With Aldehydes ...... 38 With Esters ...... 41 With Other Compounds ...... 41 Polycondensation Reactions ...... 42 Other Reactions on the Substituents ...... 42 Catalysis. Applications ...... 45

Complexes, Ions, and Salts Derived from Fe(C5HcCO-GH3h ...... 48 Complexes ...... 48 Diacetylferrocenium Ion and Its Salts ...... 51 Other Ions ...... 52

1,1 '-Dibenzoylferrocene Fe(C5H4-GO-G6H5h ...... 53 Preparation and Formation ...... 53 Physical Properties ...... 54 Solubility. Chemical Behavior ...... 58 Applications ...... 62

Other Ketones of the Type Fe(C 5H4-GO-R)2 . • ...... • . . . . . • . . • ...... • ...... • • • • • 63

Ketones of the Type R'-GO-G5H4FeC5H4-GO-R" ...... 84 Properties ...... 86 Electrochemical and Chemical Behavior ...... 87 Applications ...... 92

Ketones of the Type R'-CO-G5H4FeC5H4-R2 . . . • . • . . . • . . . . . • . . • . • ...... • • . • . . . . • 111 Properties ...... 114 Chemical Behavior ...... 115 Applications ...... 115

Ketones of the Type R'-CO-A-G5H4FeC5H4-R2 •••••••••••••••• • • • • • • • • • • • • • • • • • • • 139 Complexes and Ions Derived from 1,1 '-Ketones ...... 153 Complexes ...... 153 Ions ...... 154 Ferrocenium Ions ...... 154 Ketyls [R-GO-G5H4FeC5H4-G(R)OF ...... 154 Semidiones of the Type [R2....C5H4FeC5H4-GO=C(R')OF ...... 155

5.2.3.5.2 1, 2-Compounds ...... 156

1, 2-Diacetylferrocene C5H5FeC5H3(CO-CH3k 1, 2 ...... 156 Preparation ...... 156 Properties ...... 157 Solubility. Chemical Behavior ...... 157

Additional Ketones of the Type C5H5FeC5H3(CO-Rb-1 ,2 ...... 159

Ketones of the Type C5H5FeC5H3(CO-R-1)CO-R'-2 ...... 159

Ketones of the Type C5H5FeC5H3(CO-R'-1)R2-2 ...... 161

Ketones of the Type C5H5FeC5H3(A-GO-R'-1)R2-2 ...... 182

Ions of the Type [C5H5FeC5H3(CO=CO-R-1)0-2j2-;- ...... 186

Gmelin Handbook Fe-Org. Comp. A 8 XI

Page 5.2.3.5.3 1,3-Compounds ...... 187

Ketones of the Type C5H5FeC5H3{CO-R'·1)CQ-R"·3 ...... 187

1, 3-Diacetylferrocene C5H5FeC5H3{CO-CH3h-1, 3 ...... 187 Additional Ketones of the Type C5H5FeC5H3{CO-R'·1)CO-R"·3...... 188

Ketones of the Type C5H5FeC5H3{CO-R'·1)R2·3 ...... 188

Ketones of the Type C5H5FeC5H3{A--GO-R'·1 )R2·3 ...... 205

5.2.3.6 Carboxylic Acids and Their Salts ...... 210

5.2.3.6.1 1, 1'-Compounds ...... 21 0

1, 1'·Dicarboxyferrocene Fe{C 5HcC02Hh ...... 21 0 Preparation and Formation ...... 210 Purification and Separation ...... 212 Analysis ...... 212 Physical and Structural Properties ...... 213 57Fe Mössbauer Spectrum ...... 214 IR Spectrum ...... · ...... 214 Electronic Absorption Spectrum. Magnetic Circular Dichroism ...... 215 X-ray Photoelectron Spectroscopy ...... 215 Crystal and Molecular Structure ...... 215 Solubility. Chemical Behavior ...... 220 Solubility. Dissociation ...... 220 Mass Spectrum ...... 220 Photochemical Reactions ...... 220 Electrochemical Behavior ...... 221 Other Reactions ...... 221 Catalysis. Applications ...... 225

Ions, Salts, and Complexes Derived from Fe{C 5HcC02Hh ...... 226 Ions ...... 226 Salts and Complexes ...... 227 Alkali Metal Salts ...... 227 Other Salts ...... 229 Complexes ...... 229

Carboxylic Acids of the Type H02C-C5H4FeC5H4-R ...... 231 Chemical Behavior ...... 232

Carboxylic Acids of the Type H02C-A-C5H4FeC 5HcR2 • • • • • • • • • • • • • • • • • • • • • • • • • • • • 241 Chemical Behavior ...... 242

5.2.3.6.2 1,2-Compounds ...... 250

1, 2·Dicarboxyferrocene C5H5FeC5H3{C02Hk1, 2 ...... 250

Carboxylic Acids of the Type C5H5FeC5H3(C02H·1)R·2 ...... 251

Carboxylic Acids of the Type C5H5FeC5H3{A--G02H·1 )R2·2 ...... 259 Chemical Behavior 260

Gmelin Handbook Fe-Org. Comp. A 8 XII

Page 5.2.3.6.3 1,3-Compounds ...... 266

Carboxylic Acids of the Type C5H5FeC5H3(C02H-1)R-3 ...... 266

Carboxylic Acids of the Type C5H5FeC5H3(A-C02H-1)R2-3 ...... 269

5.2.3.7 Carboxylic Acid Esters ...... 274 5.2.3.7.1 1,1'-Compounds ...... 274 1,1 '·Di(methoxycarbonyl)ferrocene ...... 274 Preparation and Formation ...... 274 Purification. Separation ...... 275 Properties ...... 276 Solubility. Chemical Reactions ...... 279 Electrochemical Behavior ...... 279 Other Reactions ...... 280 Applications ...... 282

Carboxylic Acid Esters of the Type R'02C-C5H4FeC5H4-C02R" ...... 283

Carboxylic Acid Esters of the Type R'02C-C5H4FeC5H4-R2 . . • . • . . . • • • . • . . . • • • • • . • • . 290 Properties ...... 292 Chemical Behavior ...... 292 Applications ...... 293

Carboxylic Acid Esters of the Type R'02C-A-C5H4FeC5H4-R2 . . . • . . • • . . • . . • . . • • . . . . . 307 Chemical Behavior ...... 309

5.2.3.7.2 1,2-Compounds ...... 323

Carboxylic Acid Esters of the Type C5H5FeC5H3(C02R'-1 )R2-2 ...... 323

Carboxylic Acid Esters of the Type C5H5FeC5H3(A-C02R'-1)R2-2 ...... 332 Chemical Behavior ...... 333

5.2.3.7.3 1,3-Compounds ...... 346

Carboxylic Acid Esters of the Type C5H5FeC5H3(C02R'-1)R2-3 ...... 346

Carboxylic Acid Esters of the Type C5H5FeC5H3(A-C02R'-1)R2-3 ...... 351

5.2.3.8 Carboxylic Acid Chlorides ...... 358

5.2.3.8.1 1,1 '-Compounds ...... 358

1,1 '·Di(chlorocarbonyl)ferrocene Fe(C5H4-C0Clb ...... 358 Chemical Reactions ...... 358 With lnorganic Compounds ...... 358 With Alcohols ...... 359 With Nitrogen Compounds ...... 363 With Other Compounds ...... 368 Applications ...... 369 Other 1,1 '-Compounds ...... 370 Chemical Behavior ...... 370 Applications ...... 370

Gmelin Handbook Fe-Org. Comp. A 8 XIII

Page 5.2.3.8.2 1,2-Compounds 372

5.2.3.8.3 1,3-Compounds 373

5.2.3.9 Heterocyclic Compounds with Oxygen as Hetero Atom ...... 374

5.2.3.9.1 1,1 '-Compounds ...... 374 Epoxyethyl Derivatives ...... 374 With Five-Membered Heterocycles ...... 378

5.2.3.9.2 1,2-Compounds ...... 382

Formula Index for Ferrocene 7 and 8 ...... 385

Table of Conversion Factors ...... 418

Gmelin Handbock Fe-Org. Comp. A 8