GmeLin Handbook of Inorganic Chemistry 8th Edition Gmelin Handbook of Inorganic Chemistry 8th Edition GmeLin Handbuch der Anorganischen Chemie Achte, v6lLig neu bearbeitete Auflage Prepared GmeLin-lnstitut fOr Anorganische Chemie and issued by der Max-Planck-Gesellschaft zur F6rderung 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 1989 Gmelin-Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften ADVISORY BOARD Dr. G. Breil, Chairman (Ruhrchemie AG, Oberhausen-Holten), Prof. Dr. K. Dehnicke (Philipps Universitat Marburg), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr. H. Grunewald (Bayer AG, Leverkusen), Prof. Dr. H. Harnisch (Hoechst AG, Frankfurt/Main-Hochst), Prof. Dr. H. Noth (Universitat Munchen), Prof. Dr. H. Offermanns (Degussa AG, Frankfurt/Main), Prof. Dr. G. zu Putlitz (Universitat Heidelberg), Prof. Dr. A. Rabenau (Max-Planck-Institut fur Fest korperforschung, Stuttgart), Prof. Dr. A. Simon (Max-Planck-Institut fUr Festkorperforschung, Stuttgart), Prof. Dr. Dr. A. H. Staab (Prasident der Max-Planck-Gesellschaft, Munchen), Prof. Dr. Dr. h.c. mUlt. G. Wilke (Max-Planck-Institut fUr Kohlenforschung, Mulheim/Ruhr) DIRECTOR DEPUTY DIRECTOR Prof. Dr. Dr. h.c. Ekkehard Fluck Dr. W. Lippert CHIEF-EDITORS Dr. K.-C. Buschbeck - Dr. H. Bergmann, J. Fussel, H. Hartwig, Dr. H. Katscher, Dr. R. Keim, Dr. E. Koch, Dipl.-Phys. D. Koschel, Dr. U. Kruerke, Dr. P. Merlet, Dr. E. Schleitzer-Rust, Dr. F. Schroder, Dr. A. Slawisch, Dr. W. Topper CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF Dr. B. Baker, Dr. P. L. Bayless, Dr. V. Haase, Dr. E. F. Hockings, Dipl.-Ing. G. Kirschstein, Dr. W. F. McNamara, Dr. K. Rumpf EMERITUS MEMBER OF THE INSTITUTE Prof. Dr. Dr. E.h. Margot Becke CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Hans Bock Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.) STAFF GMELIN HANDBOOK Dr. G. Bar, D. Barthel, Dr. N. Baumann, Dr. B. Becker, Dr. W. Behrendt, D. Benzaid, Dr. L. Berg, Dipl.-Chem. E. Best, Dr. R. Bohrer, K. D. Bonn, P. Born-Heck, Dipl.-Phys. R. Bost, Dr. R. Braun, Dipl.-Ing. V. A. Chavizon, E. Cloos, Dipl.-Phys. G. Czack, I. Deim, Dipl.-Chem. H. Demmer, U. Dietz, Dipl.-Geol. R. Ditz, R. Dowideit, Dipl.-Chem. M. DroBmar, U. Duggen, Dipl. Chem. R. Durban, M. Engels, Dr. H.-J. Fachmann, Dr. J. Faust, B. Fischer, G. Funk, Dipl.-Ing. N. Gagel, Dr. D. Germeshausen, Dr. U. W. Gerwarth, Dipl.-Phys. D. Gras, Dipl.-Bibl. W. Grieser, Dr. I. Haas, Dr. R. Haubold, B. Heibel, Dipl.-Min. H. Hein, A. Heise-Schuster, H.-P. Hente, H. W. Herold, U. Hettwer, Dr. R. HeumuUer, Dr. G. Hones, Dr. W. Hoffmann, Dr. W. Huisl, B. Jager, R. Jonuschat, Dr. R. Jotter, Dr. J. von Jouanne, Dr. B. Kalbskopf, Dipl.-Chem. W. Karl, H.-G. Karrenberg, Dipl.-Phys. H. KeUer-Rudek, B. Kirchner, P. Klauck, A. Klusch, Dipl.-Chem. C. Koeppel, Dipl.-Chem. H. Kottelwesch, R. Kolb, E. Kranz, Dipl.-Chem. I. Kreuzbichler, Dr. A. Kubny, Dr. M. Kunz, Dr. W. Kurtz, M. Langer, Dr. U. Lanzendorfer, Dr. B. Leduc, Dr. A. Leonard, H. Mathis, E. Meinhard, C. Metz, K. Meyer, Dr. M. Mirbach, Dipl.-Chem. B. Mohsin, Dr. U. Neu Becker, K. Noring, Dipl.-Chem. R. Nohl, Dipl.-Min. U. Nohl, Dr. U. Ohms-Bredemann, Dr. W. Petz, I. Rangnow, Dr. B. Rempfer, Dipl.-Phys. H.-J. Richter-Ditten, Dipl.-Chem. H. Rieger, E. Rieth, A. Rosenberger, E. Rudolph, G. Rudolph, Dipl.-Chem. S. Ruprecht, Dr. B. Sarbas, Dr. H. Schafer, Dr. D. Schioberg, V. Schlicht, Dipl.-Chem. D. Schneider, Dipl.-Min. P. Schubert, Dr. K. Schucke, A. Schwarzel, Dr. B. Schwager, Dipl.-Ing. H. M. Somer, G. Strauss, Dr. G. Swoboda, Dr. U. Taubald, M. Teichmann, Dr. D. Tille, Dipl.-Ing. H. Vanecek, Dipl.-Chem. P. Velie, Dipl. Ing. U. Vetter, H.-M. Wagner, Dipl.-Phys. J. Wagner, R. Wagner, Dr. E. Warkentin, Dr. C. Weber, Dr. A. Wietelmann, Dr. M. Winter, Dr. B. Wobke, K. Wolff STAFF GMELIN ONLINE DATA SYSTEM Dr. R. Deplanque, Dr. P. Kuhn, Dr. G. Olbrich Organometallic 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) Be Organoberyllium Compounds 1 (1987) 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 Organocopper Compounds 1 (1985), 2 (1983), 3 (1986), 4 (1987), Index (1987) Fe Eisen-Organische Verbindungen A 1 (1974), A 2 (1977), A 3 (1978), A 4 (1980), A 5 (1981), A6 (1977), A 7 (1980), A8 (1985), B 1 (partly in English; 1976), Organoiron Compounds B 2 (1978), Eisen-Organische Verbindungen 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), B 13 (1988), B 14 (1989), B 15 (1989), Eisen-Organische Verbindungen C 1 (1979), C 2 (1979), Organoiron Compounds C 3 (1980), C 4 (1981), C5 (1981), C7 (1985), and Eisen B (1929-1932) Ga Organogallium Compounds 1 (1986) Ge Organogermanium Compounds 1 (1988),2 (1989) present volume Hf Organohafnium 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) Pb Organolead Compounds 1 (1987) Pt Platin C (1939) and 0 (1957) Re Organorhenium 1 (1989) Ru Ruthenium Erg.-Bd. (1970) Sb Organoantimony Compounds 1 (1981),2 (1981), 3 (1982), 4 (1986) Sc, Y, 06(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), 13 (1986), 14 (1987), 15 (1988), 16 (1988) Ta Tantal B 2 (1971) Ti Titan-Organische Verbindungen 1 (1977), 2 (1980), Organotitanium Compounds 3 (1984), 4 and Register (1984) U Uranium Suppl. Vol. E 2 (1980) V Vanadium-Organische Verbindungen (1971), Vanadium B (1967) Zr Organozirconium Compounds (1973) Gmelin Handbook of Inorganic Chemistry 8th Edition Ge Organogermanium Compounds Part 2 Ge(CH3bR and Ge(C2HSbR Compounds With 3 illustrations AUTHOR Frank Glockling University of Oxford FORMULA INDEX Bernd Kalbskopf, Uwe Nohl, Hans-JOrgen Richter-Ditten EDITORS Ulrich KrOerke, Wolfgang Petz, Christa Siebert (Maintal) CHIEF EDITOR Ulrich KrOerke Springer-Verlag Berlin Heidelberg GmbH 1989 LITERATURE CLOSING DATE: 1985 Library of Congress Catalog Card Number: Agr 25-1383 ISBN 978-3-662-07390-2 ISBN 978-3-662-07388-9 (eBook) DOI 10.1007/978-3-662-07388-9 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 "VerwertungsgeselLschaft Wort", Munich. © by Springer-Verlag Berlin Heidelberg 1988 Originally published by Springer-Verlag Berlin Heidelberg New York London Paris Tokyo in 1989 Softcover reprint of the hardcover 8th edition 1988 The use of 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. Preface The present second voLume in the organogermanium series continues the description of Ge(CH3bR compounds (Section 1.1.2.1), beginning with R = aLkenyL (Section 1.1.2.1.7, p.1) and concLuding with R = heterocycLe (Section 1.1.2.1.12, p.93). The remaining part of the voLume covers compLeteLy the type Ge(C2HSbR (Section 1.1.2.2), which is the most voLuminous of the GeR3R compounds. The arrangement of the organogermanium compounds within this series has been present ed in the preface for VoLume 1. However, it may be usefuL to repeat the following expLanations concerning the Location of compounds according to the type of the R' Ligand: The term "substituted aLkyL" stands for aLkyL Ligands containing noncarbon atoms but aLso incLudes aLkyL Ligands substituted by cycLoaLkyL, aryL, and heterocyclic groups, for exampLe, CH2C6Hs and CH2CH2CH2CSHg-cycLo, which are arranged as substituted methyL and substituted propyL, respectiveLy. In generaL, the Longest carbon chain beginning from the Ge atom deter mines the Location of a compound and is illustrated as foLLows: (a) Ge(CH3bCH2CH(OH)CH(CH3)CH3 derivative of Ge(CH3bC4Hg-n (b) Ge(CH3bCH(C6Hs)CH200CCH3 derivative of Ge(CH3bC2HS (c) Ge(C2HsbCF2COCF3 derivative of Ge(C2HsbC3Hrn (d) Ge(C6HsbCH2CH(OCH2CH=CH2)CH3 derivative of Ge(C6HsbC3Hrn ExampLes (b) and (d) show that a group beyond a heteroatom (e.g., aLLyL on oxygen) does not count for the generaL Location of a compound. Common branched hydrocarbon groups Like i-C3H7 or t-C4Hg are specifically identified. These ruLes naturally aLso appLy to compounds with aLkenyL and aLkynyL Ligands. In generaL, the arrangement is handLed somewhat flexibLy and is adapted to the scope and kind of materiaL to be described. AdditionaL expLanations are frequentLy given at the beginning of a section. As a ruLe the nomencLature recommended by IUPAC has been foLLowed. But compound names are LargeLy avoided since many of the compounds are onLy presented in tabLes and identified by their formuLas. Much of their data in the tabLes occurs in abbreviated form without units; generaL expLanations are given on p. X. The voLume concLudes with an empiricaL formuLa index (p. 297) and a Ligand formuLa index (p.329). Frankfurt am Main ULrich KrOerke November 1988 x Explanations, Abbreviations, and Units Most compounds in this volume are presented in tables in which numerous abbreviations are used and the units are omitted for the sake of brevity. This necessitates the following clarification. The formation of a compound is briefly described at the first place in the third column of a table. Evident procedures of a preparation such as hydrolysis after an organometallic reaction, evaporation of solvent, drying, etc., are usually omitted; 20°C replaces frequently the term "room temperature" in the origina!. GLC or TLC stand for gas-liquid or thin-layer chromatography. Abbreviations for solvents and other substances are as follows: AIBN for azobisisobutyro nitrile, DMF for dimethylformamide, DMSO for dimethyl sulfoxide, HMPT for hexamethylphos phoric triamide, THF for tetrahydrofuran, TMEDA for tetramethylethylenediamine. Temperatures are given in °C, 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. Terms like 80°/0.1 mean the bOiling or sUblimation point at a pressure of 0.1 Torr. Densities are given in g/cm3; dt is the density at t °C referred to water at 4°C. NMR represents nuclear magnetic resonance. Chemical shifts are given as 8 values in ppm and positive to low field from the following reference substances: Si(CH3)4 for 1H and 13C, CFC13 for 19F, H3P04 for 31p, and Ge(CH3)4 for 73Ge. Multiplicities of the signals are abbreviated as s, d, t, q (singlet to quartet), quint, sext, sept (quintet to septet), and m (multiplet); terms like dd (double doublet) and t's (triplets) are also used. Assignments referring to labeled structural formulas are given in the form C-4, H-3,S. Carbon and hydrogen atoms are labeled 1, 2, 3 ... n beginning with the Ge-bonded carbon atom. Coupling constants J in Hz appear usually in parentheses behind the 8 value, along with the multiplicity and the assignment, and refer to the respective nucleus. If a more precise designation is necessary, they are given as, e.g., nJ(C, H) or J(1, 3) referring to labeled formulas. Nuclear quadrupole resonance is abbreviated NOR, with the transitions in MHz. Optical spectra are labeled as IR (infrared), R (Raman), and UV (electronic spectrum including the visible region). IR bands and Raman lines are given in cm-1; the assigned bands are usually labeled with the symbols v for stretching vibration and 8 for deformation vibration. Intensities occur in parentheses either in the common qualitative terms (s, m, w, vs, etc.) or as numerical relative intensities. The UV absorption maxima, Amax, are given in nm followed by the extinction coefficient E (L . cm -1 . mol-1) or log E in parentheses; sh means shoulder. Photoelectron spectra are abbreviated PE, e.g., PE/He(I), with the ionization energies in eV. Hyperfine couplings of ESR spectra are given as a(N) in Gauss where N designates the respective nucleus. Solvents or the physical state of the sample and the temperature (in °C or K) are given in parentheses immediately after the spectral symbol, e.g., R (solid), 13C NMR (C6D6, SO°C), or at the end of the data if spectra for various media are reported. Common solvents are given by their formulas (C6H12 = cyclohexane) or abbreviations explained above. The fragments of mass spectra, abbreviated MS, are given in brackets followed by the relative intensity in parentheses; [M]+ is the molecular ion. XI Table of Contents Page 1.1.2 Tetraorganogermanium Compounds of the GeR3R' Type 1.1.2.1 Ge(CH3hR Compounds . .... Ge(CH3hR Compounds with R = ALkenyL . Ge(CH3hR Compounds with R = Cyclic and PoLycyclic ALkenyL . 28 Ge(CH3hR Compounds with R = ALkynyL . 51 Ge(CH3hR Compounds with R = AryL . . 68 Ge(CH3hR Compounds with R = Heterocyclic Group 93 1.1.2.2 Ge(C2HShR Compounds . . . 110 Ge(C2HshR Compounds with R = ALkyL 110 Ge(C2HShR Compounds with R = Substituted ALkyL 115 Ge(C2HshR Compounds with R = Substituted MethyL 115 Ge(C2HShR Compounds with R = Substituted EthyL . 124 Ge(C2HShR Compounds with R = Substituted PropyL 143 Ge(C2HshR Compounds with R = Substituted ALkyL Larger than PropyL 158 Ge(C2HshR Compounds with R = CycLoaLkyL and Substituted CycLoaLkyL . 167 Ge(C2HShR Compounds with R = ALkenyL . . . . . 169 Ge(C2HShR Compounds with R = Substituted ALkenyL 187 Ge(C2HshR Compounds with R = C2 ALkenyL 187 Ge(C2HShR Compounds with R = C3 ALkenyL . . . 203 Ge(C2HshR Compounds with R = C4 ALkenyL . . . 211 Ge(C2HShR Compounds with R = Cn ALkenyL where n > 4 221 Ge(C2HShR Compounds with R = Cyclic and PoLycyclic ALkenyL 229 Ge(C2HShR Compounds with R = ALkynyL . . . . . 236 Ge(C2HshR Compounds with R = Substituted ALkynyL 251 Ge(C2HshR Compounds with R = C2 ALkynyL . . . 251 Ge(C2HshR Compounds with R = Cn ALkynyL where n > 2 259 Ge(C2HSbR Compounds with R = Aromatic Group . 274 Ge(C2HSbR Compounds with R = Heterocyclic Group 285 Empirical Formula Index . 297 Ligand Formula Index . . 329 Physical Constants and Conversion Factors 397