Gmelin Handbook of lnorganic Chemistry

8th Edition

Gmelin Handbock

of lnorganic Chemistry

Prepared

and issued by

Founded by

8th Edition

Continued by

8th Edition

Gmelin Handbuch der Anorganischen Chemie

Achte, völlig neu bearbeitete Auflage

Gmelin-lnstitut für Anorganische Chemie

der Max-PLanck-GeseLLschaft

zur Förderung der Wissenschaften

Director: Ekkehard Fluck

Leopold Gmelin

8th Edition begun under the auspices of the

Deutsche Chemische Gesellschaft by R. J. Meyer

E. H. E. Pietsch and A. Kotowski, and by

Margot Becke-Goehring

Springer-Verlag Berlin Heidelberg GmbH 1988

Gmelin-lnstitut für Anorganische Chemie der Max-Planck-Gesellschaft zur Förderung der Wissenschaften

ADVISORY BOARD

Dr. G. Breit, Chairman (Ruhrchemie AG, Oberhausen-Holten), Prof. Dr. K. Dehnicke (Philipps­Universität, Marburg), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr. H. Grünewald (Bayer AG, Leverkusen), Prof. Dr. H. Harnisch (Hoechst AG, Frankfurt/Main-Höchst), Prof. Dr. H. Nöth (Universität München), Prof. Dr. H. Offermanns (Degussa AG, Frankfurt/Main), Prof. Dr. G. zu Putlitz (Universität Heidelberg), Prof. Dr. A. Rabenau (Max-Planck-lnstitut für Fest­körperforschung, Stuttgart), Prof. Dr. A. Sirnon (Max-Planck-lnstitut für Festkörperforschung, Stuttgart), Prof. Dr. Dr. A. H. Staab (Präsident der Max-Planck-Gesellschaft, München), Prof. Dr. Dr. h.c. mult. G. Wilke (Max-Planck-lnstitut für Kohlenforschung, Mülheim/Ruhr)

DIRECTOR

Prof. Dr. Dr. h.c. Ekkehard Fluck

CHIEF EDITORS

DEPUTY DIRECTOR

Dr. W. Lippert

Dr. K.-C. Buschbeck - Dr. H. Bergmann, J. Füssel, H. Hartwig, Dr. H. Katscher, Dr. R. Keim, Dr. E. Koch, Dipl.-Phys. D. Koschel, Dr. U. Krüerke, Dr. H. K. Kugler, Dr. P. Merlet, Dr. E. Schleitzer-Rust, Dr. F. Schröder, Dr. A. Slawisch, Dr. W. Töpper

CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF

EMERITUS MEMBER OF THE INSTITUTE

CORRESPONDENT MEMBERS OF THE INSTITUTE

Dr. H. C. Andersen, Dr. W. F. McNamara, Dr. V. Haase, Dipl.-lng. G. Kirschstein, Dr. K. Rumpf, Dr. U. Trobisch, Dr. B. Vance

Prof. Dr. Dr. E.h. Margot Becke

Prof. Dr. Hans Bock Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.)

STAFF GMELIN HANDBOCK

Dr. G. Bär, D. Barthel, Dr. N. Baumann, Dr. W. Behrendt, D. Benzaid, Dr. L. Berg, Dipl.-Chem. E. Best, K. D. Bonn, P. Born-Heck, Dipl.-lng. V. A. Chavizon, E. Cloos, Dipl.-Phys. G. Czack, I. Deim, Dipl.-Chem. H. Demmer, Dipl.-Geol. R. Ditz, R. Dowideit, Dipl.-Chem. M. Drößmar, Dr. D. Düster, U. Duggen, Dr. P. Eigen, M. Engels, Dr. H.-J. Fachmann, Dr. J. Faust, V. Frick, G. Funk, Dipl.-lng. N. Gagel, Dr. U. W. Gerwarth, Dipl.-Phys. D. Gras, Dipl.-Bibl. W. Grieser, Dr. I. Haas, Dr. R. Haubold, B. Heibel, Dipl.-Min. H. Hein, G. Heinrich-Sterze!, A. Heise­Schuster, H.-P. Hente, H. W. Herold, U. Hettwer, Dr. G. Hönes, Dr. W. Hoffmann, Dr. W. Huisl, R. Jonuschat, Dr. R. Jotter, Dr. J. von Jouanne, Dr. B. Kalbskopf, Dipl.-Chem. W. Karl, H.-G. Karrenberg, Dipl.-Phys. H. Keller-Rudek, B. Kirchner, A. Klusch, C. Koeppel, Dipl.-Chem. H. Köttelwesch, R. Kolb, E. Kranz, Dipl.-Chem. I. Kreuzbichler, Dr. A. Kubny, Dr. M. Kunz, Dr. W. Kurtz, M. Langer, Dr. U. Lanzendörfer, Dr. B. Ledüc, Dr. A. Leonard, Dipl.-Chem. H. List, H. Mathis, E. Meinhard, C. Metz, K. Meyer, Dr. M. Mirbach, Dipl.-Chem. B. Mohsin, Dr. U. Neu-Becker, V. Neumann, K. Nöring, Dipl.-Chem. R. Nohl, Dipl.-Min. U. Nohl, Dr. U. Ohms­Bredemann, Dr. W. Petz, I. Rangnow, 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. D. Schiöberg, V. Schlicht, B. Schmitt, Dipl.-Chem. D. Schneider, Dipl.-Min. P. Schubert, Dr. K. Schücke, A. Schwärzet, Dr. B. Schwager, Dipl.-lng. H. M. Somer, Dr. C. Strametz, Dr. G. Swoboda, Dr. U. Taubald, M. Teichmann, Dr. D. Tille, 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. C. Weber, Dr. A. Wietelmann, Dr. M. Winter, Dr. B. Wöbke, K. Wolff

STAFF GMELIN ON LI NE DATA SYSTEM

Dr. R. Froböse, Dr. P. Kuhn, Dr. G. Olbrich

Organometalllc Compounds in the Gmelin Handbook

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

Ag

Au

Be

Bi

Co

Cr

Cu

Fe

Ga Hf

Nb

Ni

Np, Pu

Pb

Pt

Ru

Sb

Sc, Y, La to Lu

Sn

Ta

Ti

u V

Zr

Silber B5 (1975)

Organogold Compounds (1980)

Organaberyllium Compounds 1 (1987)

Bismut-Organische Verbindungen (1977)

Kobalt-Organische Verbindungen 1 (1973), 2 (1973), Kobalt Erg.-Bd. A (1961), B 1 (1963), B2 (1964)

Chrom-Organische Verbindungen (1971)

Organacopper Compounds 1 (1985), 2 (1983), 3 (1986), 4 (1987), Index (1987)

Eisen-Organische Verbindungen A 1 (1974), A2 (1977), A3 (1978), A4 (1980), A5 (1981), A6 (1977), A7 (1980), A8 (1985), B1 (partly in English; 1976), Organoiron Compounds B2 (1978), Eisen-Organische Verbindungen B3 (partly in English; 1979), B4 (1978), B5 (1978), Organoiron Compounds B6 (1981), B7 (1981), B8 to B 10 (1985), B 11 (1983), B 12 (1984), Eisen-Organische Verbindungen C 1 (1979), C2 (1979), Organoiron Compounds C3 (1980), C4 (1981), C5 (1981), C7 (1985), and Eisen B (1929-1932)

Organagallium Compounds 1 (1986)

Organahafnium Compounds (1973)

Niob B4 (1973)

Nickel-Organische Verbindungen 1 (1975), 2 (1974), Register (1975), Nickel B3 (1966), and C1 (1968), C2 (1969)

Transurane C (partly in English; 1972)

Organolead Compounds 1 (1987)

Platin C (1939) and D (1957)

Ruthenium Erg.-Bd. (1970)

Organoantimony Compounds 1 (1981), 2 (1981), 3 (1982), 4 (1986)

06 (1983)

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) present volume

Tantal B2 (1971)

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

Uranium Suppt. Vol. E2 (1980)

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

Organozirconium Compounds (1973)

Grnelin Handbock of lnorganic Chemistry

AUTHORS

FORMULA INDEX

EDITOR

8th Edition

Sn

Organatin Compounds

Part 15

Dibutyltin-Oxygen Compounds

With 5 illustrations

by Herbert Schumann and lngeborg Schumann

Herbert Schumann, lngeborg Schumann Technische Universität Berlin

Edgar Rudolph, Gmelin-lnstitut, Frankfurt am Main

Ulrich Krüerke, Gmelin-lnstitut, Frankfurt am Main

Springer-Verlag Berlin Heidelberg GmbH 1988

LITERATURE CLOSING DATE: 1985

Library of Congress Galalog Card Number: Agr 25-1383

ISBN 978-3-662-06614-0 ISBN 978-3-662-06612-6 (eBook) DOI 10.1007/978-3-662-06612-6

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 Iee is payable to "Verwertungsgesellschaft Wort", Munich.

© by Springer-Verlag Berlin Haideiberg 1988 Originally published by Springer-Verlag, Berlin · Heidelberg · New York · Tokyo in 1988 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 proteelive Laws and regulations and therefore free for generat use.

Typesetting

Preface

The present volume continues the series on "Organotin Compounds" which first appeared in 1975 and now comprises a collection of fifteen volumes. The overallplan of the series has been given in the preface of Volume 1. The present Volume 15 continues the description of the mononuclear organotin compounds with tin-oxygen bonds (Chapter 1.4.1 ). Treatment of organotin compounds with tin-sulfur, -selenium, and -tellurium bonds appeared earlier in Chapters 1.4.2 to 1.4.4 of Volumes 9, 1982, and 10, 1983.

Volume 15 contains R2Sn-oxygen compounds with R = butyl, iso-butyl, sec-butyl, and tert-butyl, covering the Literature completely to the end of 1985. Additional volumes describing tin-oxygen compounds with other R2Sn and RSn groups will follow in the near future.

Abbreviations and symbols are explained on pp. X/XI along with other remarks.

We thank Prof. Dr. Dr. h. c. Ekkehard Fluck and his coworkers at the Gmelin Institute for their excellent cooperation. ln particular, we thank Dr. Ulrich Krüerke for his accurate and sympathetic editing, Mr. Edgar Rudolph for preparing the index, Dr. Grant for reading the English text, and Mr. Hans-Georg Karrenberg for drawing the numerous formulas and molec­ular structures. We thank Mrs. Ellen Redlinger, Miss Susanne Schumann, and Miss Stefanie Schumann for their meticulous handling of the Literature index and the members of the chemical department of the Library at the Technische Universität Berlin for their assistance in searching and acquiring the references from the Literature.

Berlin-Lichtenrade November 1987

Herbert Schumann lngeborg Schumann

X

Explanation&, Abbreviation&, and Units

Many compounds in this volume are presented in tables in which numerous abbreviations are used and the units are omitted for the sake of conciseness. This necessitates the following clarification.

The term "special" in the second column of the tables indicates preparative methods which are described under the further information section following the table.

Temperetures 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 subl. for SUblimation. Terms like 80°/0.1 mean the boiling or SUblimation point at a pressure of 0.1 Torr. Densities D are given in g/cm3. Dc and Dm distinguish calculated and measured values, respectively.

NMR represents nuclear magnetic resonance. Chemical shifts are given as ö values in ppm and positive to low field from the following reference substances: Si(CH3)4 for 1H and 13C, BF3 · O(C2H5b for 11 8, CFCLa for 19F, H3P04 for 31 P, and Sn(CH3)4 for 119Sn. 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) arealso used. Assignments referring to Labeted structural formulas are given in the form C-4, H-3,5. Garbon and hydrogen atoms of the C-bonded ligands (C4H9 in this volume) are Labeted a., ß, y, and ö. Coupling constants J in Hz appear usually in parentheses behind the ö value, along with the multiplicity and the assignment, and refer to the respective nucleus. lf a more precise designation is necessary, they are given as, e.g., "J(C, H) or J(1, 3) referring to Labeted formulas. The coupling to the two nuclei 117Sn and 119Sn is written as J(Sn,X) = A/B. A single value, J(Sn,X) = A, always refers to the 119Sn nucleus.

Nuclear quadrupole resonance is abbreviated NQR, with the transitions in MHz.

Mössbauer spectra are represented by 119Sn-y; both the isomer shift ö (vs. BaSn03 or Sn02 at room temperature) and the quadrupole splitting Li are given in mm/s; the experimental error has generally been omitted. Other reference substances for ö are indicated after the numerical value, e.g., ö = -0.31 (a.-Sn).

Optlcal spectra are Labeted 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 Labeted with the symbols v for stretching vibration and ö for deformation vibration. lntensities 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 bythe extinction coefficientE (L · cm-1 • mol- 1) orlogEin parentheses; sh means shoulder.

Photoelectron spectra are abbreviated PE, e.g., PE/He(l), with the ionization energies in eV.

Solvents or the physlcal 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, 50°C), or at the end of the data if spectra for various media are reported. Common solvents are given by their formula (C6H12 = cyclohexane) except THF, DMF, and HMPT, which represent tetrahydrofuran, dimethylformamide, and hexamethylphosphoric triamide, respectively.

XI

The data of mass spectra, abbreviated MS, are given as m/e, relative intensity in parenthe­ses, and fragment ions in brackets; [M] + is the molecular ion.

References, quoted in the last column, are occasionally also placed in the first and second column if statements from different sources must be distinguished.

Figures give only selected parameters. Barred bond lengths (in Ä) or angles are mean values for parameters of the same type.

Table of Contents

1.4.1.2 Diorganotin-Oxygen Compounds . . . . . . . . . . . .

1.4.1.2.1 Diorganotin-Oxygen Compounds of the R2Sn(OR'h Type .

Dibutyltin-Oxygen Compounds, (C4H9hSn(ORh .

Dibutyltin Dihydroxide, (C4H9hSn(OHh . . . .

XIII

Page

Dibutyltin Bis(Organyl Oxides), (C4H9hSn(ORh 2 Dibutyltin Bis(Alkoxides), (C4H9hSn(ORh 2 Dibutyltin Bis(Alkenyl Oxides), (C4H9hSn(ORh 28 Dibutyltin Bis(Aryl Oxides), (C4H9hSn(ORh . . 32 Dibutyltin Bis(Organyl Oxides), (C4H9hSn(ORh with R = Heterocycle 39 Dibutyltin Alkoxides of the (C4H9hS'n-0-R-6 Type . . . . . . . . . 45

Dibutyltin Derivatives of ß-Diketones, -Ketoacidesters or -amides, and -Ketimines . 96 Dibutyltin Biscarboxylates, (C4H9bSn(OOCRh . . . . . . . . . . . . . . 103

Dibutyltin Biscarboxylates, (C4H9bSn(OOCRh with R = Unsubstituted Alkyl 103 Dibutyltin Diformiate, (C4H9bSn(OOCHb . 103 Dibutyltin Diacetate, (C4H9bSn(OOCCH3h 104

Synthesis, Properties, and Reactions 104 Taxicity and Biocidal Properties . . . 110 Uses . . . . . . . . . . . . . . . . 111

Dibutyltin Biscarboxylates, (C4H9bSn(OOCRb with R = C2H5 , C3H7 , C4H9 , t-C4H9 ,

C5H11 , C6H13, and i-C6H13 . . . . . . . . . . . . . . . . . . 127 Dibutyltin Dicaprylate, (C4H9bSn(OOCC7H15)2, and

Dibutyltin Bis(2-ethylhexanoate), (C4H9bSn(OOCCH(C2H5)C4H9b . . . . . . 129 Dibutyltin Biscarboxylates, (C4H9hSn(OOCRb with R = C8H17, i-C8H17, C9H19, and

neo-C9H19 . . . . . . . . . . . . . . 134 Dibutyltin Dilaurate, (C4H9bSn(OOCC11 H23h 135

Synthesis, Properties, and Reactions 135 Taxicity and Biocidal Properties . . . . 139 Uses . . . . . . . . . . . . . . . . . 141

Dibutyltin Biscarboxylates, (C4H9hSn(OOCRh with R = C11 H23 , C13H27 , C15H31 ,

C17H35 , C20H41 , and C21 H43 . . . . . . . . . . . . . . . . . . 250 Dibutyltin Biscarboxylates, (C4H9hSn(OOCRh with R = Cycloalkyl . 253

Dibutyltin Biscarboxylates, (C4H9bSn(OOCR)2 with R = Substituted Alkyl or Cycloalkyl . . . . . . . . . . . . . . . . . . . . . . . . . . 254

Dibutyltin Biscarboxylates, (C4H9bSn(OOCRh with R = Alkenyl or Cycloalkenyl 267

Dibutyltin Biscarboxylates, (C4H9bSn(OOCRh with HOOCR = Unsaturated Monocarboxylic Acid . . . . . . . . . . . . . . . . . . . . 267

Dibutyltin Biscarboxylates of the Type (C4H9hSn(OOC-CX=CX-COYRh with X= H, CL, or Br and Y = 0 or S . . . . . . . . . . . . . . . . 272

Dibutyltin Biscarboxylates, (C4H9bSn(OOCR)2 with R = Cycloalkenyl 284 Dibutyltin Biscarboxylates, (C4H9hSn(OOCRh with R =Aryl . . . . 286 Dibutyltin Biscarboxylates, (C4H9hSn(OOCRh with R = Heterocycle. . 298

XIV

Dibutyltin Oxalate, (C4H9hS'nOOC-C06, and Dibutyltin Dicarboxylates (C4H9hS'nOOC-R-C06 Type ..... . Dibutyltin Oxalate, (C4H9hS'nooc-co6 Dibutyltin Maleate, (C4H9hs'nOOCCH=CHC06

Synthesis, Properties, and Reactions Toxicity and Biocidal Uses . . . . . . . . Uses ................. .

Other Dibutyltin Dicarboxylates of the (C4H9hS'n....,o=o=c""""'-R""""---:;;;cc;;oc::l6 Type

Dibutyltin Oxycarboxylates, (C4H9hS'nOOCR6 . . . . . Dibutyltin Carbonic Acid Esters, (C4H9hSn(OOCORh, and

Dibutyltin Acylimines, (C4H9hSn(OCR=NR'h . . . . . Dibutyltin Peroxides, (C4H9hSn(OORh or (C4H9hS'nOOR6, and

Page of the

301 301 301 301 303 304 321 331

332

Dibutyltin Peroxycarboxylates, (C4H9hSn(OOCORh . . . . 334 Dibutyltin Dihalogenates . . . . . . . . . . . . . . . . . 336 (C4H9)2Sn(ON02h, (C4H9hSnON(C6H4CH3-4)COCON(C6H4CH3-4)6, and

Other Compounds Containing the (C4H9)2Sn(0Nh Unit. . . . . . . . . . . . . 337 (C4H9)2SnOS02, (C4H9hSnOS03 , (C4H9hS'n03S(CH2)6S026, and Dibutyltin Compounds

of the (C4H9hSn(OSOn(X,Y))2 Type with n = 1 or 2. . . . . . . . . . . . . . 346 Dibutyltin Borate and Dibutyltin Compounds Containing the (C4H9hSn(OB)2 Unit . 350

Dibutyltin Compounds with Sn-0-Si Bonds . . . . . . . . . 352 Dibutyltin Compounds with Sn-0-P Bonds . . . . . . . . . . 353

Dibutyltin Compounds Containing the (C4H9hSn(OP)2 Unit . . 353 Dibutyltin Compounds of the (C4H9hS'nOP(O,S)(R,OR)6 Type . 358 Other Dibutyltin Compounds with Sn-0-P Bonds . . . . . 360

Dibutyltin Compounds with Sn-0-As Bonds. . . . . . . . . 361 Dibutyltin Compounds Containing the (C4H9hSn(OAsh Unit 361 Dibutyltin Compounds of the (C4H9hS'n0As(O)(R)6 Type . 362 Other Dibutyltin Compounds with Sn-0-As Bonds . 367

Dibutyltin Compounds Containing Sn-0-Se Bonds. 368 Dibutyltin Compounds Containing Sn-0-Ti Bonds . . 368

Diisobutyltin-Oxygen Compounds, (i-C4H9hSn(ORh and (i-C4H9hS'n0-R-6 369

Di-sec-butyltin-Oxygen Compounds, (sec-C4H9hSn(ORh . . . . . . . . 372

Di-tert-butyltin-Oxygen Compounds, (t-C4H9hSn(ORh and (t-C4H9hs'n0-R-6 372

Empirical Formula Index . 381

Ligand Formula Index . . . 401

Table of Conversion Factors 441