Table Of Content!
2 Hol 10 No I 18 Ar I 36 Kr I 54 Xo I 86 Rn I H.'3
;
!
2 5 6 7 8
I H 9 F 17 CI 35 Br 53 I 85 AI
3 9 10 ll 12 71
8 0 16 5 34 Se 52 To 84 Po 71 Lu 03Lr
1
7 N 4 15 P 16 33 AI 17 51 Sb 18 83 Bi 19 70 Yb 10271 No
6 C 14 14 Si 15 32 45 Ge 50 Sn 45 82 Pb 47 69 Tm ~: 71
n System Numbers 5 B 13 , 13 I AI 35 3D 29 31 36 60 32 Cu Zn Ga 47 48 49 In Ag 51 37 Cd 33 79 80 81 Au 62 TI 38 Hg 34 66 67 68 Ho Er Dy 99IOD 71 ~: 71 71 E. Fm
meli 57 65 68 71
e G 28 Ni 46 Pd 78 PI 65 Tb :~
with th 27 58 Co 45 64 Rh 77 Ir 67 64 Gd 9671 Cm
ments 26 59 Fe 44 63 Ru 76 66 0. 63 Eu 9571 Am
Elethe ! 25 56 Mn 43 Tc 69 75 70 Re 62 Sm 9471 Pu
0' Table iI 24 52 Cr 42 53 Mo 74 54 W 61 Pm 9371 Np
die 48 49 50 71 5 5
erio I ! 23 V 41 Nb 73 Ta 105 60 Nd 92 U
P
, I I I I I ! 21 22 Sc 39 41 Ti 39 40 42 Y 39 Zr 72 57** HI43 La 39 89*** 104 71 Ac 40 58 59 Pr Co 9091 44 51 Pa Th
4 B26 0 12 27 Mg 20 28 Ca 38 29 Sr 56 Ba 3D 88 31 Ra an idel 39 nides
I H 2 3 LI 20 11 21 Na 19 • K 22 37 24 Rb 55 C.25 87 Fr *lanth **Acti
~ f • f a ,. l f ,. 1 , f I i I
Gmelin Handbook 01 Inorganic Chemistry
8th Edition
Organometallic Compounds in the GmeLin Handbook
The foLLowing Listing indicates in wh ich voLumes these compounds are discussed or are
referred to:
Ag SiLber 85 (1975)
Au OrganogoLd Compounds (1980)
8i 8ismut-Organische Verbindungen (1977)
Co KobaLt-Organische Verbindungen 1 (1973),2 (1973), KobaLt Erg.-8d. A (1961), 81
(1963), 82 (1964)
Cr Chrom-Organische Verbindungen (1971)
Cu Organocopper Compounds 1 (1985), 2 (1983)
Fe Eisen-Organische Verbindungen A 1 (1974), A2 (1977), A3 (1978), A4 (1980), A5
(1981), A6 (1977), A 7 (1980), A8 (1985), 81 (partLy in EngLish; 1976), Organoiron
Compounds 82 (1978), Eisen-Organische Verbindungen 83 (partLy in EngLish;
1979), 84 (1978), 85 (1978), Organoiron Compounds 86 (1981), 87 (1981), 88 to
810 (1985), 811 (1983), 812 (1984), Eisen-Organische Verbindungen C1 (1979),
C2 (1979), Organoiron Compounds C3 (1980), C4 (1981), C5 (1981), C7 (1985),
and Eisen 8 (1929-1932)
Hf Organohafnium Compounds (1973)
Nb Niob 84 (1973)
Ni NickeL-Organische Verbindungen 1 (1975), 2 (1974), Register (1975), NickeL 83
(1966), C 1 (1968), C2 (1969)
Np, Pu Transurane C (partLy in EngLish; 1972)
Pt PLatin C (1939) and D (1957)
Ru Ruthenium Erg.-8d. (1970)
Sb Organoantimony Compounds 1 (1981),2 (1981), 3 (1982)
Sc, Y, D6 (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 82 (1971)
Ti Titan-Organische Verbindungen 1 (1977), 2 (1980) 3 (1984), 4 and Register (1984)
U Uranium SuppL. VoL. E2 (1980)
V Vanadium-Organische Verbindungen (1971), Vanadium 8 (1967)
Zr Organozirconium Compounds (1973)
Grnelin Handbook
of Inorganic 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 1985
Gmelin-Institut für Anorganische Chemie
der Max-Planck-Gesellschaft zur Förderung der Wissenschaften
ADVISORY BOARD
Dr. J. Schaafhausen, Chairman (HoechstAG, Frankfurt/Main-Höchst), Dr. G. Breil (Ruhrchemie
AG, Oberhausen-Holten), Dr. G. Broja (Bayer AG, Leverkusen), Prof. Dr. G. Fritz (Universität
Karlsruhe), Prof. Dr. N.N. Greenwood (University of Leeds), 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
Institut 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-Institut für
Kohlenforschung, Mülheim/Ruhr)
DIRECTOR DEPUTY DIRECTOR
Prof. Dr. Dr. h.c. Ekkehard Fluck Dr. W. Lippert
CHIEF-EDITORS
Dr. K.-C. Buschbeck - Dr. H. Bergmann, J. Füssel, B. Heibel, Dr. H. Katscher, Dr. R. Keim,
Dipl.-Ing. G. Kirschstein, Dipl.-Phys. D. Koschel, Dr. U. Krüerke, Dr. H.K. Kugler, Dr. P. Merlet,
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.-Ing. 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.-Ing. N. Gagel, E. Gerhardt, Dr. U.w. Gerwarth, M.-L. Gerwien,
Dipl.-Phys. D. Gras, C. Gorr, Dr. V. Haase, H. Hartwig, Dipl.-Min. H. Hein, G. Heinrich
Sterzel, H.-P. Hente, HW. 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,
K. Meyer, 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. Rudolph, G. Rudolph, Dipl.- Chem.
S. Ruprecht, Dr. R.C. Sangster, V. Schlicht, Dipl.-Chem. D. Schneider, Dipl.-Min. P. Schubert,
A. Schwärzel, Dipl.-Ing. H.M. Somer, E. Sommer, M. Teichmann, Dr. W. Töpper, Dipl.-Ing.
H. Vanecek, Dipl.-Chem. P. Veli6, Dipl.-Ing. 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. K. Rumpf, Dr. U. Trobisch, Dr. J.L. Grant
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.)
Grnelin Handbook
of Inorganic Chemistry
8th Edition
Fe
Organoiron
Compounds
Part B9
Mononuclear Compounds 9
With 27 iLLustrations
AUTHOR Adolt Slawisch
EDITORS Jürgen Faust, Johannes Füssel, Marlis Mirbach
CHIEF EDITOR Adolt Slawisch
Springer-Verlag Berlin Heidelberg GmbH 1985
LlTERATURE CLOSING DATE: 1983
IN SOME CASES MORE RECENT DATA HAVE BEEN CONSIDERED
Library 01 Congress Catalog Card Number: Agr 25-1383
ISBN 978-3-662-06929-5 ISBN 978-3-662-06927-1 (eBook)
DOI 10.1007/978-3-662-06927-1
This work is subject to copyright. AU rights are reserved, whether the whole ar part 01 the material is concerned, specificaUy
those of transLatian, 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,
alee is payable ta "Verwertungsgesellschaft Wart", Munich.
© by Springer-Verlag Berlin Heidelberg 1985
Originaily published by Springer-Verlag,Berlin . Heidelberg . New York· Tokyo in 1985
Saftcaver reprint 01 the hardcaver 8th editian 1985
The use of general descriptive names, trade marks, etc. in the Gmelin Handbook, even if the former are nat especiaUy identilied,
is not ta be taken as a sign that such names, as understoad by the Trade Marks and Merchandise Marks Act, may accardingly
be used Ireely by anyone.
Preface
The present voLume is a continuation of Series 8 on the mononucLear organoiron com
pounds and describes 545 compounds. It covers the Literature compLeteLy to the end of
1983 and incLudes many references to the Literature up to mid-1984.
This voLume continues the description of mononucLear organoiron derivatives by treating
compounds of the type 4LFe(COh where 4L incLudes seven-, eight-, and nine-membered
ring. systems. OnLy a few Larger rings of the 4LFe(COh type compounds are known, and
they are aLso incLuded. In the symboL mLn, n is the number of organic Ligands L in the
compound, and m is the number of Fe-C bonds formed from an L Ligand as aLready expLained
in the prefaces to "KobaLt-Organische Verbindungen" 1, New SuppL. Ser., VoL. 5, 1973, and
"NickeL-Organische Verbindungen" 1, New SuppL. Ser., VoL. 16, 1975.
Se ries 8 so far comprises voLumes 81 to 812, and a survey of this series has been
given in the preface to 87 (1981).
Much of the data, particuLarLy in tabLes, is given in abbreviated form without dimensions;
for expLanation see p. VIII. AdditionaL remarks, if necessary, are given in the heading of
the tabLes.
A formuLa index for voLumes 88, 89, and 810 wiLL be given in "Organoiron Compounds"
810.
Frankfurt AdoLf SLawisch
September 1985
VIII
Remarks on Abbreviations and Dimensions
Many compounds in this volume are presented in tables in wh ich numerous abbreviations
are used, and the dimensions are omitted for the sake of conciseness. This necessitates
the following clarification:
The prefixes ende (same side of ring to that occupied by Fe) and exo (opposite side
of ring) are used to denote stereochemistry of the complexes; see also pp. 44.
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
subl. for sublimation.
NMR represents nuclear magnetic resonance. Chemical shifts are given as 0 values
in ppm; reference substances and signs for 0 are shown in the scheme below:
increasing field -+
0=0 for
1H + Si(CH3)4 Coupling constants J, in Hz, are given as
118 + 8F3· O(C2Hsh J (A, 8) or as J (1,3) and refer to label ied
13C + Si(CH3)4 structural formulas.
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 t's (triplets)
are also used. Assignments referring to labe lied structural formulas are given in the form
C-4, H-3,5. The numbering deviates in some cases from official nomenclature so that corre
sponding values for compounds in the same chapter can be more easily compared.
Mössbauer spectra are represented by S7Fe-y and 119Sn_y: both the isomer shift 0 (vs.
Na2[Fe(CN)sNOl or 8aSn03 at room temperature) and the quadrupole splitting ~ are given
in mm/s; the experimental error has generally been omitted. Other reference substances
for 0 are indicated after the numerical value, e.g., 0=0.23 (Fe).
Optlcal spectra are labelled 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 labe lied with the symbols v for stretching vibration and 0 for deformation
vibration whereas unlabelled bands belong to CO stretching vibrations. Intensities occur
in parentheses either in the common qualitative terms (s, m, w, vs, br, etc.) or as numerical
relative intensities; str., def., pol., and dp mean stretching, deformation, polarized, and
depolarized, respectively. The CO stretching force constant and CO, CO interaction constant
(in mydn/A) are denoted as k and k', respectively. The UV absorption maxima, Amax' are
given in nm followed by the extinction coefficient E (L· cm-1 . mol-1) or log Ein parentheses;
sh means shoulder.
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 (CeDe,
50°C). Common solvents are given by their formula (cyclo-CeH12=cyclohexane) except
THF, which represents tetrahydrofuran.
Figures give only selected parameters. Bond lengths (in A) or angles are mean values.
IX
Table 01 Contents
Organoiron Compounds, Part B
Mononuclear Compounds 9
Page
Remarks on Abbrevlatlons and Dimensions VIII
1.4.1.4.1.2.4 4L Is a Seven-Membered Ring System 1
4L is a Heterocyclic Ring System 2
4L is an Isocyclic Ring . . . . . . . . . . 34
4L is Cyclohepta-1,3-diene ..... . 34
4L is a Substituted Cyclohepta-1,3-diene 37
4L is Cycloheptatriene 102
C7HaFe(C°la . . . . . . . . . 102
C7HaFe(C°laAlX3 . . . . . . . 116
4L is a Substituted Cycloheptatriene 116
4L is a Monosubstituted Cycloheptatriene 116
4L is a Disubstituted Cycloheptatriene . . 144
Other Substituted Cycloheptatrieneirontricarbonyl Complexes 179
4L is a Cyclohepta-1,4-diene ........ . 197
1.4.1.4.1.2.5 4L is an Eight-Membered Ring System 207
4L is a Cyclooctadiene 208
4L is a Cyclooctatriene 219
4L is a Cyclooctatetraene 230
CaHaFe(COh and Its AlBr3 Adduct 230
Preparation and Formation of CaHaFe(COh 230
Physical Properties of CaHaFe(COh . . . . 234
Chemical Behavior and Uses of CaHaFe(COh 241
The Adduct CaHaFe(COhAlBr 3 . . . . . . 253
4L is a Substituted Cyclooctatetraene . . . . 253
1.4.1.4.1.2.6 4L is a Nlne-Membered Ring System 279
1.4.1.4.1.2.7 4L is a Ring System Greater than Cg 282
Table of Conversion Factors 285
