Embed Size (px)
Citation preview
INORGANIC SYNTHESES
Volume 26
Board of Directors
JOHN P. FACKLER, JR. BODIE E. DOUGLAS University of Pittsburgh JAY H. WORRELL University of South Florida SMITH L. HOLT, JR. Oklahoma State University STANLEY KIRSCHNER Wayne State University JEANNE N. SHREEVE HARRY R. ALLCOCK Pennsylvania State University HERBERT D. KAESZ University of California L o s Angeles ALVIN P. GINSBERG AT&T Bell Laboratories
Texas A & M University
University of Idaho
Future Volumes
27 ALVIN P. GINSBERG AT&T Bell Laboratories 28 RUSSELL N. GRIMES University of Virginia 29 ROBERT J. ANGELIC1 Iowa State University 30 LEONARD V. INTERRANTE Rensselaer Polytechnic Institute 31 ALAN H . COWLEY University of Texas at Austin 32 MARCETTA Y. DARENSBOURG Texas A & M University
International Associates
MARTIN A. BENNETT FAUSTO CALDERA220 University of Pisa E. 0. FISCHER Technical University, Munich JACK LEWIS Cambridge University LAMBERTO MALATESTA University of Milan RENE POILBLANC University of Toulouse HERBERT W. ROESKY University of Gottingen F. G. A. STONE GEOFFREY WILKINSON AKIO YAMAMOTO
Australian National University, Canberra
University of Bristol Imperial College of Science and Technology, London
Tokyo Institute of Technology, Yokohama
Editor-in-Chief HERBERT D. KAESZ Department of Chemistry and Biochemistry University of California, Los Angeles
INORGANIC SYNTHESES
Volume 26
A Wiley-Interscience Publication JOHN WILEY & SONS
New York Chichester Brisbane Toronto Singapore
Published by John Wiley & Sons, Inc.
Copyright 0 1989 Inorganic Syntheses, Inc.
All rights reserved. Published simultaneously in Canada.
Reproduction or translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc.
Library of Congress Catalog Number: 39-23015
ISBN 0-471-50485-8
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
PREFACE
Jean’ne M. Shreeve stated in the Preface to Volume 24 of this series that, “preparative chemistry is the heart of chemistry.” However, chemistry plays an important role in many scientific disciplines. Focusing on inorganic and metalorganic compounds for example, we note that metal complexes are playing an important role in autoradiography and cancer chemotherapy in the field of medicine. Mixed metal oxides are leading to new superconductors. Metal organic compounds are precursors to new materials, and volatile metal complexes are used in chemical vapor deposition of thin films in surface science, physics, and electronics. The same is true for the role of new and useful substances in organic chemistry, polymer chemistry, biochemistry, molecular biology, and so on. Thus, I am prompted to generalize and to suggest that synthesis is a central discipline in science.
Synthesis can be a difficult practice, as any novice to the field will attest. Inorganic Syntheses is an attempt to identify compounds of general interest, to select the best procedures for their preparation from generally available starting materials, and to verify that the procedures can be carried out successfully as written. I hope the scientific community finds this volume to be a useful collection, and continues to submit procedures and accept manu- scripts for checking in continuing volumes of this series.
Contents. Submissions have been grouped into chemically related categories represented by the chapter headings. Because many of the submissions also incorporate syntheses of starting materials, some procedures are located outside of the category in which they would separately belong. For example, there are syntheses of compounds of the main group elements that appear beyond Chapter I , such as procedures numbered 10.A, 1O.C, 26, 21, 48.A, 50.A, 62.A, and 70.A. Similarly, procedures for some mononuclear complexes are located in Chapter 5, see 44.A, 59.A, 62.B, and 62.C.1, while that of a tetrarhenium derivative is located in Chapter 3, see 19.D.
~~ ~
Previous volumes of Inorganic Syntheses are available. Many of the volumes originally published by McGraw Hill, Inc. are available from R. E. Krieger Publishing Co., Inc., P.O. Box 9542, Melbourne, FL 32901. Please write this publisher for a current list. Volumes out of print with John Wiley & Sons, Inc. are also available from Krieger Publishing. Recent back volumes can be obtained from John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158. Please write the publisher for a current list of available volumes.
vii
... viii Preface
Within each chapter the submissions are ordered, as far as possible, according to the columns of the periodic table. In Chapter 5, homopolynu- clear complexes are presented first, followed by heteropolynuclear com- pounds. Many submissions, however, contain several parts. As a consequence, the location of some of the procedures can not adhere to this general sequence.
Acknowledgments. Like editors of previous volumes of this series, I am indebted to many colleagues for contributions to this work. First there are Wolfgang Beck in Munich, Ekkehard Lindner in Tubingen, and John R. Shapley in Urbana, who assisted me in the selections and solicitations for three special collections: transition metal complexes containing weakly bonded anions (Chapter 3), metalocyclic complexes (Chapter 4), and polynuclear transition metal complexes (Chapter 5), respectively. Each has contributed a preface for the chapter he helped to form, following the pattern set in Volume XI1 when Alan G. MacDiarmid invited E. C. Ashby and myself to form a chapter on metal hydrides. As a consequence of such efforts, more than two-thirds of this volume consists of invited preparations.
The above-mentioned three valued colleagues and friends are also thanked for further participating as submitters and checkers. Indeed all the individuals so listed deserve thanks for the contributions that are the contents of this volume.
Editorial work was assisted by evaluations and comments on submitted manuscripts by members of Inorganic Syntheses. Foremost and unfailing in this group were J. C. Bailar, Jr., T. Moeller, D. F. Shriver, R. J. Angelici, and the late W. C. Fernelius. Advice on nomenclature was routinely provided by T. E. Sloan and W. H. Powell of Chemical Abstracts Service.
To all of the above-mentioned colleagues, and to my family from whom I have had to withdraw for many hours of solitary work, I extend my wholehearted thanks.
HERBERT D. KAESZ
Los Angeles, California August 1988
NOTICE TO CONTRIBUTORS AND CHECKERS
The Znorganic Syntheses series is published to provide all users of inorganic substances with detailed and foolproof procedures for the preparation of important and timely compounds. Thus the series is the concern of the entire scientific community. The Editorial Board hopes that all chemists will share in the responsibility of producing Znorganic Syntheses by offering their advice and assistance in both the formulation of and the laboratory evaluation of outstanding syntheses. Help of this kind will be invaluable in achieving excellence and pertinence to current scientific interests.
There is no rigid definition of what constitutes a suitable synthesis. The major criterion by which syntheses are judged is the potential value to the scientific community. For example, starting materials or intermediates that are useful for synthetic chemistry are appropriate. The synthesis also should represent the best available procedure, and new or improved syntheses are particularly appropriate. Syntheses of compounds that are available commer- cially at reasonable prices are not acceptable. We do not encourage the submission of compounds that are unreasonably hazardous, and in this con- nection, less dangerous anions generally should be employed in place of perchlorate.
The Editorial Board lists the following criteria of content for submitted manuscripts. Style should conform with that of previous volumes of Inorganic Syntheses. The introductory section should include a concise and critical summary of the available procedures for synthesis of the product in question. It should also include an estimate of the time required for the synthesis, an indication of the importance and utility of the product, and an admonition if any potential hazards ate associated with the procedure. The Procedure should present detailed and unambiguous laboratory directions and be written so that it anticipates possible mistakes and misunderstandings on the part of the person who attempts to duplicate the procedure. Any unusual equipment or procedure should be clearly described. Line drawings should be included when they can be helpful. All safety measures should be stated clearly. Sources of unusual starting materials must be given, and, if possible, minimal standards of purity of reagents and solvents should be stated. The scale should be reasonable for normal laboratory operation, and any problems involved in
ix
x Notice to Contributors and Checkers
scaling the procedure either up or down should be discussed. The criteria for judging the purity of the final product should be delineated clearly. The section on Properties should supply and discuss those physical and chemical characteristics that are relevant to judging the purity of the product and to permitting its handling and use in an intelligent manner. Under References, all pertinent literature citations should be listed in order. A style sheet is available from the Secretary of the Editorial Board. Authors are requested to avoid procedures involving perchlorate salts due to the high risk of explosion in combination with organic or organometallic substances. It is also suggested if at all possible to avoid the use of benzene as a solvent owing to its carcinogenic properties.
The Editorial Board determines whether submitted syntheses meet the general specifications outlined above, and the Editor-in-Chief sends the manuscript to an independent laboratory where the procedure must be satisfactorily reproduced.
Each manuscript should be submitted in duplicate to the Secretary of the Editorial Board, Professor Jay H. Worrell, Department of Chemistry, University of South Florida, Tampa, FL 33620. The manuscript should be typewritten in English. Nomenclature should be consistent and should follow the recommendations presented in Nomenclature of Inorganic Chemistry, 2nd ed., Butterworths & Co., London, 1970, and in Pure and Applied Chemistry, Volume 28, No. 1 (1971): Abbreviations should conform to those used in publications of the American Chemical Society, particularly Inorganic Chemistry.
Chemists willing to check syntheses should contact the editor of a future volume or make this information known to Professor Worrell.
TOXIC SUBSTANCES AND LABORATORYHAZARDS
Chemicals and chemistry are by their very nature hazardous. Chemical reactivity implies that reagents have the ability to combine. This process can be sufficiently vigorous as to cause flame, an explosion, or, often less immediately obvious, a toxic reaction.
The obvious hazards in the syntheses reported in this volume are delineated, where appropriate, in the experimental procedure. It is impossible, however, to foresee every eventuality, such as a new biological effect of a common laboratory reagent. As a consequence, all chemicals used and all reactions described in this volume should be viewed as potentially hazardous. Care should be taken to avoid inhalation or other physical contact with all reagents and solvents used in procedures described in this volume. In addition, particular attention should be paid to avoiding sparks, open flames, or other potential sources that could set fire to combustible vapors or gases.
A list of 400 toxic substances may be found in the Federal Register, Vol. 40, No. 23072, May 28,1975. An abbreviated list may be obtained from Inorganic Syntheses, Volume 18, p. xv, 1978. A current assessment of the hazards associated with a particular chemical is available in the most recent edition of Threshold Limit Values for Chemical Substances and Physical Agents in the Workroom Environment published by the American Conference of Govern- mental Industrial Hygienists.
The drying of impure ethers can produce a violent explosion. Further information about this hazard may be found in Inorganic Syntheses, Volume 12, p. 317. A hazard associated with the synthesis of tetramethyldiph- osphine disulfide [lnorg. Synth., 15,186 (1974)] is cited in Inorganic Syntheses, Volume 23, p. 199.
xi
CONTENTS
1.
2.
3.
4.
5.
6.
7.
Chapter One COMPOUNDS OF THE MAIN GROUP ELEMENTS AND THE LANTHANIDES
Potassium Tetradecahydrononaborate( I -) . . . . . . . . . . . . . . . . . . . . . . .
Bromotrimethylsilane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Trimeth ylphosphine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Phosphorus Trifluoride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
($-Cyclopentadieny1)lanthanide Complexes from the Metallic Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Tris(~5-cyclopentadienyl)(tetrahydrofuran)neodymium(III). B. Tris(~5-cyclopentadienyl)(tetrahydrofuran)samarium(III) . . . C. Bis(q5-cyclopentadienyl)( 1,2-dimethoxyethane)-
ytterbium(I1) . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . , . . . . . . . . . . . . . . . .
Chapter Two MONONUCLEAR TRANSITION METAL COMPLEXES Part I
Ammonium [( 1R)-(endo, anti)]-3-bromo-l, 7-dimethyl-2- 0x0 bicyclo [ 2.2.11 heptane-7-met hanesulfonate, and Synthesis and Resolution of cis-Dichlorobis( 1,2-ethanediamine)- chromium(II1) Chloride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Ammonium [( 1R)-(endo, anti)]-3-bromo- 1,7-dimethyl-2-
oxobicyclo[2.2.1] heptane-7-methanesulfonate [ammonium ( + ),,,-a-bromocamphor-n-sulfonate]. . . . . . . . . . . . . . . . . . . . . . . .
B. cis-Dichlorobis( 1,2-ethanediamine)chromium(III) Chloride Monohydrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
C. ( + ),,,-A-cis-Dichlorobis( 1,2-ethanediamine)- chromium(II1) Chloride Monohydrate . . . . . . . . . . . . . . . . . . . . . . .
Organometallic Complexes of Isomeric Acyl Isocyanides Chromium Carbonyl (Acyl Isocyanide) and (Acyl Cyanide) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
4
7
12
17 20 21
22
24
25
27
28
31 ...
XI11
xiv Contents
A . (Benzoyl isocyanide)dicarbonyl(q6-methyl-
B . (Benzoyl isocyanide)pentacarbonylchromium(O) ..... C . (Benzoyl cyanide)pentacarbonylchromium(O) ........
benzoate)chromium(O) .................................
8 . Diammonium pentachlorooxomolybdate(V)
9 . Carbyne Complexes of Tungsten ........................... A . Pentacarbonyl[(diethylamino)methylidyne]tungsten
Tetrafluoroborate ...................................... B . trans-Tetracarbonyl[(diethylamino)methylidyne]-
(isocyanato)tungsten ...................................
10 . (2. 2.Dimethylpropylidyne)tungsten(VI) Complexes and Precursors for Their Syntheses ............................. A . Met hox ytrimet h ysilane ................................
.....
.....
...
...
...
...
...
...
...
...
B . Trichlorotrimethoxytungsten ................................. C . (2, 2.Dimethylpropyl)magnesium Chloride ................... D . Tris(2.2.dimethylpropyl)(2. 2.
dimeth ylpropylid yne)tungsten(VI) ............................ E . Trichloro( 1.2.dimethoxyethane)(2.2.dimethy 1.
pro pylidyne)tungsten(VI) ......................................
11 . Zerovalent Iron Isocyanide Complexes ............................ A . Tetracarbonyl(2-isocyano- 1. 3-dimethylbenzene)iron(O) ..... B . Tricarbonylbis(2.isocyano.l, 3-dimethylbenzene)iron(O) .... C . Dicarbonyltris(2.isocyano.1, 3.dimethylbenzene)iron(O) ..... D . Carbonyltetrakis(2-isocyano- 1, 3.dimethylbenzene)iron(O) . . E . Pentakis(2.isocyano.1, 3.dimethyIbenzene)iron(O) ...........
12 . Tetracarbonyliron(0) Complexes Containing Group V Donor Ligands ..............................................................
B . Other Tetracarbonyl(Gr0up V Donor Ligand) Iron(0) Complexes .....................................................
A . Tetracarbonyl(triphenylphosphine)iron(O) ....................
13 . cis-Tetraamminedihaloruthenium(II1) Halide Complexes ......... A . cis-Tetraamminedichlororuthenium(II1) Chloride ........... B . cis-Tetraamminedibromoruthenium(II1) Bromide ...........
14 . (q4- 1. 5.Cyclooctadiene)ruthenium(II) Complexes ................. A . Di.p.chloro(q4.1. 5.cyclooctadiene)rutheniurn(II) . . . . . . . . . . . .
32 34 35
36
40
40
42
44 44 45 46
47
50
52 52 54 56 57 57
59 61
61
65 66 67
68 69
B .
C .
D .
E .
F .
G .
H .
I .
J .
K .
Contents
Bis(acetonitrile)dichloro(q4.1. 5- cyclooctadiene)ruthenium(II) .................................. Bis(benzonitrile)dichloro(q4.1. 5- cyclooctadiene)ruthenium(II) .................................. Bis(acetonitrile)dibromo(q4.1. 5- cyclooctadiene)ruthenium(IT) .................................. Bis(benzonitrile)dibromo(q4- 1. 5.
Tris(acetonitrile)chloro(q4- 1. 5. cyclooctadiene)ruthenium(II) Hexafluorophosphate( 1 -) ... Tris( acetonitri1e)br omo( q4 . 1. 5 . cyclooctadiene)ruthenium(II) Hexafluorophosphate( 1 -) ... Tetrakis(acetonitrile)(q4.1. 5-cyclooctadiene)ruthenium(II) bis[hexafluorophosphate( 1 -)I ............................... (q4- 1. 5.Cyclooctadiene)tetrakis(hydrazine)ruthenium(II) bis[tetraphenylborate( 1 - )] ................................... (q4.1. 5-Cyclooctadiene)tetrakis(methylhydrazine) ruthenium(II)bis[hexafluorophosphate( 1 - )] ................ (q4.1. 5-Cyclooctadiene)tetrakis(methylhydrazine) ruthenium(II)bis[tetraphenylborate( 1 -)] ....................
cyclooctadiene)ruthenium(II) ..................................
1 5 . Pentacarbonylhydridorhenium .....................................
16 . Organometallic Fluoro Complexes ................................ A . Tetrakis[tricarbonylfluororhenium(I)]tetrahydrate .......... B . (2,2 '.Bipyridine)tricarbonylfluororhenium(I) ................. C . (2,T .Bipyridine)tricarbonyl(phosphorodifluoridato)
rhenium(1) ...................................................... D . DicarbonylbisC 1 , 2-ethanediylbis(diphenylphosphine)]
fluoromolybdenum(I1) hexafluorophosphate( 1 - ) ...........
17 . (Tetrahydrothiophene)gold(I) or Gold(II1) Complexes ............
B . (Pentafluorophenyl)(tetrahydrothiophene)gold(I) ............ C . Tris(pentafluorophenyl)(tetrahydrothiophene)gold(III) ......
A . Chloro(tetrahydrothiophene)gold(I) ..........................
D . Benzyltriphenylphosphonium
E . Bis[ 1, 2-phenylenebis(dimethylarsine)]gold(I)
F . (Pentafluoropheny1)-p-
Chloro(pentafluorophenyl)aurate(I) ...........................
bis(pentafluorophenyl)aurate(I) ...............................
thiocyanato(triphen ylphosphene)digold(I) ....................
xv
69
70
70
71
71
72
72
73
74
74
77
81 82 82
83
84
85 86 86 87
88
89
90
xvi Contents
Chapter Three MONONUCLEAR TRANSITION METAL COMPLEXES Part 11. COMPLEXES WITH WEAKLY BONDED ANIONS
Preface W. Beck ....... ......................... .................... .
and -tungsten Complexes.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18. Carbonyl(q5-cyclopentadienyl)(tetrafluoroborato)molybdenum
A.
B.
C.
D.
E.
F.
Tricarbonyl( q 5-
cyclopentadienyl)(tetrafluoroborato)molybdenum and -tungsten . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . Dicarbonyl(q5- cyclopentadienyl)(tetrafluoroborato)(triphenylphosphine)- molybdenum and -tungsten, MCp(CO),(PPh,)(FBFJ (M = Mo, W). . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tricarbon yl( q 5-cyclopentadienyl) ( q -et hene)mol y bdenum- (1 +)tetrafluoroborate(l -). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Carbonyl(q5- cyclopentadienyl)bis(diphenylacetylene)molybdenum( 1 + ) tetrafluoroborate(1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Carbonyl(~5-cyclopentadienyl)(diphenylacetylene) (triphenylphosphine)molybdenum( 1 + )tetrafluoroborate- (1 -) . . . . . . . . . . . . I .. ........... . . ...... ... .. . . . . .......... . ..... . (Acetone) (tricarbon yl) ( q '-cyclopen tadieny1)molyb- denum(1 +) and -tungsten(l +)tetrafluoroborate(l -). . . . . . .
19. Pentacarbonyl(tetrafluoroborato)rhenium and -manganese and Reactions Thereof.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Pentacarbonylmethylrhenium ................................. B. Pentacarbonyl(tetrafluoroborato)rhenium(I) ................. C. Pentacarbonyl(q2-ethene)rhenium( 1 + )tetrafluoro-
borate( 1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D. Di-p3-(carbon dioxide)octadecacarbonyltetrarhenium . . . . . .
20. Manganese(1) and Rhenium(1) Pentacarbonyl(trifluoromethane- sulfonato) Complexes . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Pentacarbonyl(trifluoromethanesulfonato)manganese(I),
Mn(C0),(03SCF3) ............................................ B. Pentacarbonyl(trifluoromethanesulfonato)rhenium(I),
Re(CO),(O3SCF3) .............................................
21. Iridium(I11) Complexes with the Weakly Bonded Anions [BFJ, and [OSO,CF,]- .......................................
92
96
96
98
102
102
1 04
105
106 107 108
110 111
113
114
115
117
Contents xvii
A.
B.
C.
D.
Carbon ylchlorohydrido(tetrafluoroborato)bis- (triphenylphosphine)iridium(III) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 17 Carbonylchlorometh yl(tetrafluoroborato)bis- (triphenylphosphine)iridium(III) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 18 Chloro(dinitrogen)hydrido(tetrafluoroborato)bis- (triphenylphosphine)iridium(III) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 19 Carbonylhydridobis(trifluoromethanesu1fonato)bis- (triphenylphosphine)iridium(III) .............................. 120
22. Dihydridobis(solvent)bis(triphenylphosphine)iridium(III) Tetrafluoroborates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. (q4- 1,5-Cyclooctadiene)bis(triphenylphosphine)iridium(I)
Tetrafluoroborate(1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Bis(acetone)dihydridobis(triphenylphosphine)iridium(III)
Tetrafluoroborate( 1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Diaquadihydridobis(triphenylphosphinefiridium(II1)
Tetrafluoroborate( 1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D. ( 1,2-Diiodobenzene)dihydridobis(triphenylphosphine)-
iridium(II1) Tetrafluoroborate( 1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . .
23. cis-Chlorobis(triethy1phosphine)- (trifluoromethanesulfonato)platinum(II). . . . . . . . . . . . . . . . . . . . . . . . . . . .
24. Acetonitrile Complexes of Selected Transition Metal Cations . . . A. Tetrakis(acetonitrile)palladium(II) bis(tetrafluorob0rate)-
B. cis-Tetrakis(acetonitrile)dinitrosylmolybdenum(II)
C. cis-Tetrakis(acetonitrile)dinitrosyltungsten(II)
(1 -) . . . . . . . . . . . . . . . . . . . . * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . .
bis(tetrafluoroborate)(l -). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
bis(tetrafluoroborate)(l -). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
25. The Formation of the Hydrido(methanol)bis(triethyl- phosphine)platinum(II) Cation and Its Reactions with Unsaturated Hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . A. trans-Hydrido(methanol)bis(triethylphosphine)platinum(II)
bis(trifluoromethanesulfonate)( 1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . . B. ~-Hydrido-hydridophenyltetrakis(triethylphosphine)di-
platinum(I1) tetraphenylborate( 1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . C. cis(3-Methoxy-3-oxo-IcO-propyl-KC')bis(triethylphos-
phine)platinum(II) tetraphenylborate( 1 - ) . . . . . . . . . . . . . . . . . . . D. (~3-Cyclooctenyl)bis(triethylphosphine)platinum(II) tetra-
phenylborate( 1 -). . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
122
122
123
124
125
126
128
128
132
133
134
135
136
138
139
xviii Contents
E. trans-Chloro(cis-l,2-diphenylethenyl)bis(triethyl- phosphine)platinum(II) . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter Four MONONUCLEAR TRANSITION METAL COMPLEXES Part III. METALLOCYCLIC COMPLEXES
Preface E. Lindner ...... .. . ................... ... ............ ....... 26. Main Group Metal (Li or Mg) o-PhenylenedimethylEo-
C6H4(CHJ2 or o-C,H,{t]H(SiMe,)},] Transfer Reagents . . . . . . A. The di-Grignard Reagent of o-bis(Chloromethy1)-
benzene, 1 .. .... ............................... ... ............. . B. o-Bis[ (trimethylsilyl)methyl] benzene . . . . . . . . . . . . . . . . . . . . . . . . . C. p-[(cr,a’, 1,2- h a, a’, 1,2-h)-O-bis-
[trimethylsilyl)methyl]-benzene] bis(N, N’-tetramethyl-l,2- ethanediamine)-dilithium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
27. Cyclometallated Organolithium Compounds . . . . . . . . . . . . . . . . . . . . . A. [2-[(Dimethylamino)methyl]phenyl]lithium ................. B. [2-[(Dimethylamino)methyl]-5-methylphenyl]lithium . . . . . . C. [2-[(Dimethylamino)phenyl]-methyl]lithium ................ D. (Diethyl ether)[8-[(dimethylamino)-l-naphthyl]lithium.. . . .
28. Metallation of Aromatic Ketones with Pentacarbonylmethylmanganese(1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Pentacarbonylmethylmanganese(1) and (2-Acetylphenyl-
C, 0)tetracarbonylmanganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Octa~arbonyl-l-k-~C, 2~~C-p-[carbonyl-lrcC:2~[0-
(3-diphenylphosphino- 1 rcP)-o-pheny1ene-2rcC1 ] - dimanganese, 5.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
29. Cyclo-Cotrimorization of Phosphinothioyls with Alkynes. Phosphinothioyl-containing Manganese Analogs of Cyclopen- tadiene and Bicycloheptadienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Dimethylphosphine sulfide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Octacarbonylbis-p-(dimethylphosphinothioyl-P:S)-
dimanganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Tetracarbonyl[2-(dimethylphosphinothioyl)- 172-bis-
(methoxycarbony1)ethenyl-C‘ : S)manganese . . . . . . . . . . . . . . . . . . D. Tricarbonyl[q4-3, 6-dihydr0-3,4,5,6-
tetrakis(methoxycarbonyl)-2,2-dimethyl- 2H- 1,2-thiaphosphorin-2-ium-3,6-diyl]manganese. . . . . . . . . .
140
142
144
146 148
148
150 152 152 153 154
155
156
158
161 162
162
163
165
Contents xix
E. F. Tricarbonyl[q4-2, 5-dihydro-2,3,4,5-
Tetramethyl thiophenetetracarboxylate . . . . . . . . . . . . . . . . . . . . . .
tetrakis(methoxycarbony1)-1, 1 -dimethyl- 3H-phosphol- 1 -ium-2,5-diyl]manganese.. . . . . . . . . . . . . . . . . . . .
166
167
30. Tetracarbonyli [2-(dipheny1phosphino)phenyll- hydroxymethyl-C, Plmanganese. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
31. Cyclometallation Reactions.. , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Benzylpentacarbonylmanganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Tetracarbonyl[2-(phenylazo)phenyl-C', N'lmanganese
and p-(azodi-l,2-phenylene-C1, N': C", N')-octacarbonyl- dimanganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
C . Bis[p-ch10ro-[2-(pheny1azo)pheny1-C1, N2]palladium]. . . . . . 175 D. Tricarbonyl[2-(phenylazo)phenyl)-C', N'lcobalt . . . . . . . . . . . . 176 E. cis-Bis(benzo[h]quinolin-IO-yl-C'o, N' )dicarbonyl-
ruthenium(I1). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177 F. (q5-Cyclopentadienyl)[2-[diphenoxyphosphino)-
oxylphenyl-C, Pltriphenylphosphite-P)ruthenium(II) . . . . . . . 178
171 172
32. ($-Hexamethy1benzene)ruthenium Complexes Containing Hy- dride and ortho-Metallated Triphenylphosphine . . . . . . . . . . . . . . . . . . 180 A. Chloro(q6-hexamethylbenzene)(hydrido)(triphenyl-
phosphine)ruthenium(II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 1 B. [6-Diphenylphosphino)phenyl-C' , P] ($-hexamethyl-
benzene)(hydrido)ruthenium(II) ............................... 182
33. An Osmium Containing Benzene Analog, 6s(CSCHCHCHCH)(CO)(PPh,),, Carbonyl (5-thioxo- 1,3-pentadiene-l,5-diyl-C1, C5, S)bis(triphenyl- phosphine)osmium and Its Precursors.. . . . . . . . . . . . . . . . . . . . . . . . . . . . 184 A. Dichlorotris(triphenylphosphine)osmium(II) ................. 184 B. Dichloro(thiocarbonyl)tris(triphenylphosphine)osmium(II) . 185 C. Dihydrido(thiocarbonyl)tris(triphenylphosphine)-
osmium(I1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186 D. Carbonyl(thiocarbonyl)tris(triphenylphosphine)osmium(O). . 187 E. Carbonyl(5-thioxo-l,3-pentadiene-l, 5-diyl-C', C5, S)-
bis(triphen ylphosphine)osmium, 6s(CSCHCHCHCH)(C0)(PPhJ2 ........................... 188
(tripheny1phosphine)cobalt with Various Substituents.. . . . . . . . . . . 189 A. Chlorotris(tripheny1phosphine)cobalt ........................ 190
34. (1,3-butadiene-1, 4-diyl)(q5-Cyclopentadieny1)-
xx Contents
B. (q5-Cyclopentadienyl)bis(triphenylphosphine)cobalt.. ....... C . (q5-Cyclopentadienyl) [ 1, l’-(q2-l, 2-ethynediy1)dibenzenel-
(tripheny1phosphine)cobalt and ($-cyclopentadieny1)- (methyl-3-phenyl-q2-2-propynoate)(triphenylphosphine)- cobalt. ..........................................................
butadiene- 1,4-diyl)(triphenylphosphine)cobalt. ..............
butadiene- 1, 4-diyl)(q5-cyclopentadienyl)(triphenyl- phosphine)cobalt and [ 1,3-bis(methoxycarbony1)-2- methyl-Cphenyl- 1,3-butadiene- 1, 4-diyl)(q5- cyclopentadien y1)-(tripheny1phosphine)- cobalt.. .........................................................
D. (q5-Cyclopentadienyl)(2,3-dimethyl-l, 4-diphenyl-l,3-
E. [l, 4-Bis(methoxycarbonyI)-2methyl-3-phenyl-1,3-
35. An Iridium(II1) Complex Containing Cyclometallated Tri- phenylphosphine Formed by Isomerization of an Iridium(1) Triphenylphosphine Complex ...................................... A. Chlorotris(triphenylphosphine)iridium(I) ..................... B. (OC-6-53)Chlorol: (2-diphenylphosphino)phenyl-C' , PI-
hydridobis(triphenylphosphine)iridium(III) ..................
36. Nickel-Containing Cyclic Amide Complexes. ..................... A. [2-Methylpropanamidato(2-)-C3, N ] (tricyclohexyl-
phosphine)nickel(II), (tcyp) &iCH,CH(CH,)COhH.. ...... B. CButanamidato(2-)C4, N ] -
(tricyclohex ylphosphine)nickel(II), $JiCH,CH,CH,COfiH (tcyp). ...............................
37. Six-Membered Cyclopalladated Complexes of 2-Benzylpyridine. A. Bis(pacetato)bis[2-(2-pyridinylmethy1)phenyl-C1, N ] -
dipalladium(I1). ................................................ B. Di-p-chloro-bis[2-(2-pyridinylmethyl)phenyl-C ' , N ] -
dipalladium(I1). ................................................ C. Chloro( 3,5-dimethylpyridine) [2-(2-pyridinylmethyl)-
phenyl-C‘ , N ] palladium(I1) ..................................
38. Cyclopalladated Compounds.. .....................................
phenyl-C, N)dipalladium(II) ................................... A. Di-p-chloro-bis[2-[(dimethylamino)methyl]-
B. Di-p-chloro-bis(8-quinolylmethyl-C, N ) - dipalladium(I1) .................................................
191
192
195
197
200 20 1
202
204
205
206
208
208
209
210
21 1
212
213
Contents xxi
Chapter Five POLYNUCLEAR TRANSITION METAL COMPLEXES
Preface J. R. Shapley .......... ............ . . . ............. .......... Ditungsten Tetracarboxylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Tungsten Tetrachloride [WCI,],. . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Tetrakis(trifluoroacetato)ditungsten(II).
W,(0,CCF3),(W~W) ........................................ C . Tetrakis(2,2-dimethylpropanoato)ditungsten(II).
W,(O,C-t-Bu),(W~W) ....................................... D. Tetrakis(acetato)ditungsten(II). W,(O,CCH,),(WAW). . . . .
40. Diphenylphosphino-Bridged Dimanganese Complexes. . . . . . . . . . . A. (p-Diphenylphosphino)-p-hydrido-bis(tetracarbonyl-
manganese)(Mn-Mn) ........................................ B. p-Nitrido-bis(triphenylphosphorus)( 1 + ) (p-diphenyl-
phosphino)bis(tetracarbonylmanganate)(Mn-Mn)( 1 -) . . . C. Heterometallic Trinuclear Clusters
1. Octacarbonyl-ltc4C, 2tc4C(p-diphenylphosphino- 1 : 2tcP)-(triphenylphosphine-3tcP)-triangulo- dimanganesegold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
carbony1manganese)fMn-Mn) . . . . . . . . . . . . . . . . . . . . . . . . . .
39.
2. (I.c-Chloromercurio)(~i-diphenylphosphino)-bis(tetra-
A.
B.
C.
D.
E.
41. Preparation of Some Bimetallic p-(qL-C, 0) Acetyl Complexes . . Dicarbonyl(qS-cyclopentadienyl)(tetrahydrofuran)iron
215 219 22 1
222
223 224
225
226
228
229
230
23 1
Hexafluorophosphate .......................................... 232 (p-Acetyl-C : 0)-Bis(dicarbony1-qs-cyclopentadien y1iron)- (1 +) Hexafluorophosphate( 1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235 (p-Acetyl-2~C' : 1tcO-tricarbonyl-lic2C, 2tcC-bisC 1 :2(q5- cyclopentadienyl)] (triphenylphosphine-2~P)diiron( 1 + ) Hexafluorophosphate(1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . (p-Acetyl-2rcC': ltcO)-pentacarbonyl-~~C, 2tc2 C-bisC1 :2(qs- cyclopentadienyl)]molybdenumiron( 1 + ) Hexa- fluorophospate(1 -). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (p-Acetyl-2~C' : 1 tcO)-tetracarbonyl- 1 tc3 C, 2tc2C-bis[ 1 : 2(qs-cyclopentadienyl)(triphenyl- (qs-cyclopentadien y1)phosphine- 1 xP)- molybdenumiron( 1 +) Hexafluorophosphate( 1 -) . . . . . . . . . . .
237
239
241
42. Trinuclear Metal Complexes ....................................... 243 A. Nonacarbonyl dihydrido-p3-thio-triiron . . . . . . . . . . . . . . . . . . . . . 244 B. Nonacarbonyl-p,-thio-dicobaltiron .......................... 245
xxii Contents
43. Bis[p-nitrido-bis(triphenylphosphorus)( 1 +)[p4- carbido-dodecacarbonyltetraferrate(2 - )] .........................
44. Dinuclear Ruthenium(I1) Carboxylate Complexes ................ A. Di-p-chloro(q4-bicyclo[2.2. l]hepta-2,5-diene)ruthenium(II)
Polymer ........................................................ B. (q4-Bicyclo[2.2. llhepta-2, 5-diene)bis(q3-2-propeny1)-
ruthenium( 11). .................................................. C . Di-p-chloro-(q4-cycloocta- lf5-diene)rutheniurn(II)
Polymer ........................................................ D. (q4-Cycloocta-1, 5-diene)bis(q3-2-propenyl)ruthenium(II). ...
1,5-diene)(trifluoroacetato)ruthenium(II)] ................... E. p-Aqua-bis-(p-trifluoroacetato)-bis[q4-cycloocta-
F. p-Aqua-bis-(p-chloroacetato)-bis[(chloroacetato)(q4-cyclo- octa-l,5-diene)ruthenium(II)]. ................................
G. p-Aqua-bis-(p-trichloroacetato)-bis[(q4-bicyclo[2.2.l]- hepta-2,5-diene)(trichloroacetato)ruthenium(II)] ............
45. Polynuclear Ruthenium Complexes.. .............................. A. Dodecacarbonyltriruthenium, Ru,(CO),,. ................... B. Dodecacarbonyltetra-p-hydrido-tetraruthenium,
R u ~ ( ~ - H ) ~ ( C O ) , 2 ..............................................
46. A Phosphino Bridged Ruthenium Cluster: Nonacarbonyl- p-hydrido-( p-diphenylphosphino)triruthenium(O) .................
47. [p-Nitrido-bis(triphenylphosphorus)( 1 +)] [deca- ca rbony l - l~~ C, 2k3 C, ~K~C-yhydr ido - l :2~’H-bis- (triethylsily1)-1 K S i , 1 KSi)triangulo-trimthenate( 1 -)I.. ............
48. Tri- and Tetranuclear Carbonyl-Ruthenium Cluster Com- plexes Containing Isocyanide, Tertiary Phosphine, and Phos- phite Ligands. Radical Ion-Initiated Substitution of Metal
A. Sodium Benzophenone Ketyl Solution.. ..................... B. Undecacarbonyl(dimethylphenylphosphine)triruthenium,
Ru,(CO), ,(PMe,Ph) .......................................... C. Decacarbonyl(dimethylphenylphosphine)(2-isocyano-
2-methylpropane)triruthenium, Ru,(CO),,(CN-t-Bu)-
Cluster Carbonyl Complexes Under Mild Conditions. ...........
(PMe,Ph) ...................................................... D. Decacarbonyl[methylenebis(diphenylphosphine)]-
triruthenium, Ru,(CO)~~[(P~,P),CH,] .....................
246
249
250
25 1
253 254
254
256
256
259 259
262
264
269
27 1 273
273
275
276
Contents xxiii
E . [p-Ethynediylbis(diphenylphosphine)]bis[undeca-
F . Undecacarbonyltetrahydrido[tris(4-methylphenyl) phos-
G . Decacarbonyl(dimethy1phenylphosphine)tetra-
carbonyltriruthenium]. { (Ru3(CO), 1)2[p-C2(PPh2)2]} .....
phiteltetraruthenium. Ru,H,(CO), . [P(OC&,hk.p), ] ....
Ru,H,(CO). .(PMe. Ph) [ P(0C. H,Me.p). ] ................. hydrido[tris(4-methylphenyl) phosphite] tetraruthenium.
49 . Carbido-carbonyl Ruthenium Cluster Complexes ................ A . p6-Carbido-heptadecacarbonylhexaruthen~um ............... B . p5-Carbido-pentadecacarbonylpentaruthenium .............. C . Disodium or Bis[p-nitrido-bis-
(triphenylphosphorus)(l +)] Salts of [p,.Carbidotetradecacarbonylpentaruthenate( 2-)] ........
50 . Nitrido-Ruthenium Cluster Complexes ............................ A . p-Nitrido-bis(triphenylphosphorus)( 1 +)azide. PPNCN,] . . . B . p-Nitrido-bis(triphenylphosphorus)( 1 + )hexadeca-
carbonylnitridohexaruthenate( 1 -). [PPN] [Ru,N(CO),, ] . C . p-Nitrido-bis(triphenylphosphorus)( 1 + )tetraadeca-
carbonylnitridopentaruthenate( 1 -). [PPN] [Ru,N(CO),, ]
5 1 . Some Useful Derivatives of Dodecacarbonyltriosmium .......... A . (Acetonitri1e)undecacarbonyltriosmium ...................... B . Undecacarbonyl(pyridine)triosmium ......................... C . Bis(acetonitri1e)decacarbonyltriosmium ......................
52 . Dodecacarbonyltetra-p-hydrido-tetrahedr~-tetraosmium
53 . High Nuclearity Carbonyl Cluster Complexes of Osmium .......
carbonylpentaosmate(2 - ) .....................................
D . Octadecacarbonyldihydridohexaosmium .....................
A . Octadecacarbonylhexaosmium ............................... B . Bis[p-nitrido-bis(triphenylphosphorus)( 1 + ) pentadeca-
C . Bis[p-nitrido-bis(triphenylphosphorus)( 1 +)] octadeca- carbonylhexaosmate(2 - ) ......................................
54 . Thioosmium Clusters ............................................... A . (p.Benzenethiolato)decacarbonyl...hydrido.triosmium, 1 .. B . p3.Carbonyl.nonacarbonyl.p,.thio.triosmium. 2 ............ C . Nonacarbonyldi.p,.thio.triosmium. 3 ........................ D . Tridecacarbonyldi.p,.thio.tetraosmium. 4 ................... E . Dodecacarbonyldi.p,.thio.tetraosmium. 5 ...................
277
277
278
280 281 283
284 286 286
287
288
289 290 291 292
293
295 295
299
300 301
303 304 305 306 307 307
xxiv
55.
56.
57.
58.
59.
60.
61.
Contents
F. Analogous Selenido Clusters.. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Tris(q5-cyclopentadienyl)bis(p,-phenyl- methy1idyne)-tricobalt . . . . . . . . . . . . . . , , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Bis(tetramethy1ammonium) Hexa-p-carbonyl-hexacarbonyl- hexanickelate(2-), [N(CHJ,],[Ni6(CO)6(p-CO),j] . . . . . . . . . . . . . . .
Bis(tetrabuty1ammonium) Hexa-p-carbonyl-hexa- carbonylhexaplatinate(2-), [N(C,H,),],[Pt 6(CO)6(pCO)61
Preparation of the Carbonyl Platinum Anions,
A. Bis(tetraethy1ammonium) PentakisCtri-p-carbonyl-
B. Bis(tetraethy1ammonium) TetrakisCtri-p-carbonyl-tri-
C. Bis(tetraethy1ammonium) TrisCtn-p-carbonyl-tricarbonyl-
[Pt3(C0),],Z - (n = 3-5). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . * . . . .
tricarbonyltriplatinatel(2 -), [N(C,H5),]2[Pt3(Co)6]5.. . . .
carbonyltriplatinate](2-), [N(C,H5),]2[Pt,(CO)6]4.. . . . . .
triplatinate] (2 - ), [N(C, H5)J2 [PtJ(co)6] 3 . . . . . . . . . . . . . . . . . Synthesis of Gold-Containing Mixed-Metal Cluster Complexes. A. Chloro(triphenylphosphine)gold, AuCI(PPh,) , , . . . . . . . , . . . , . B. p3-Oxo-[tris(triphenylphosphinegold)] (1 +)tetra-
fluoroborate( 1 -), [O(Au(PPh,) >,] [BF,] . . . . . . . . . . . . . . . . . . . C. Dodecacarbonyltris(tripheny1phosphine)cobalttrigoldtri-
ruthenium, Au, CoRu,(CO) ,(PPh ,),. . . . . . . . . . . . . . . . . . . . . . . . Mercury-Bridged Transition Metal Cluster Derivatives and Their Precursor.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . , . . . . . . A. Nonacarbonyl-p,-( K : q2 : q2-3,3-dimethyl- 1 -butynyl)-
p-hydrido-triangulo-triruthenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. 1. Nonacarbonyl-p,-(lc:q2:q2-3, 3-dimethyl-l-butyny1)-
p-iodomercurio-tr iangulo-triruthenium . . . . . . . . . . . . . . . . . .
dimethyl- 1 -butynyl)-triangulo-triruthenium . . . . . . . . . . . . . . C. p,-Mercurio-bis-[Nonacarbonyl-p3-(~:q2:q2-3, 3-
dimethyl- 1 -butynyl)-triangulo-triruthenium] . . . . . . . . . . . . . . , . . D. Nonacarbony1-p3-(lc:q2:q2-3, 3-dimethyl-l-butyny1)-
p-{ [tricarbonyl(q’-cyclopentadienyl)molybdio]- mercurio>-triangulo- triruthenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. p-(Brornomercurio)-nonacarbonyl-p,-(~:q~: q2-3,3-
308
309
312
316
319
320
32 1
322
324 325
326
327
328
329
3 30
331
333
333
Heterobinuclear Nonacarbonyl Complexes and Hydride Com- plexes of Iron-Chromium, Iron-Molybdenum, and Iron- Tungsten ............................................................. 335
Contents xxv
A. 1-Nitrido-bis(triphenylphosphorus)( 1 + )tetra-
B. p-Nitrido-bis(triphenylphosphorus)( 1 +)-
C. Bis[p-nitrido-bis(triphenylphosphorus)( 1 + )]
carbonyl hydridoferrate( 1 -). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
nonacarbonylhydridoferrate tungstate( 1 - ) . . . . . . . . . . . . . . . . . .
nonacarbonylchromateferrate( 1 - ) . . . . . . . . . . . . . . . . . . . . . . . . . . . 62. Cyclopentadienylsodium and some Mono-, Tri-, and Tetranu-
clear Metal Carbonyl Derivatives and Cluster Complexes.. . . . . . A. Cyclopentadienylsodium - 1,2-dimethoxyethane. . . . . . . . . . . . B. Sodium tricarbonyl(q5-cyclopentadienyl)metallates, DME
solvates, Na[M(CO),(qS-C,Hs)].2DME (M = Cr, Mo, or W), . . .. . ......... . .. . . . ....... ... . . . ...... ...
1. Bis(benzonitri1e)-dichloroplatinum ....................... 2. A Linear Dimetallic Platinum Complex .......... ....... Planar Tetranuclear Clusters with Mixed-Metal Cores M’,Mo,(C~H~)~(CO),(PP~,),, (M’ = Pd or Pt) 1. Hexacarbonylbis(q5-cyclopentadienyl)bis(triphenyl-
C. A Linear Dimetallioplatinum Complex
D.
phosphine)dimoly bdenumdiplatinum, [Pt,Mo,(qs-CSHs)2(Co),(PPh,),l . . . . . . . . . . . . . . . . . . . . . .
2. Hexacarbonylbis(q5-cyclopentadienyl)bis(tri- pheny1phosphine)dimoly bdenumdipalladium, [Pd,Mo,(qs-C,H,),(CO)6(PPh,),l ......................
63. Mixed Trinuclear Dicobaltiron and Dicobaltruthenium Cluster Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Nonacarbonyl-1,-thio-dicobaltiron, FeCo,(CO),S.. . . . . . . . . B. Nonacarbonyl-p,-thio-dicobaltruthenium, RuCo,(CO),S . . C. Nonacarbonyl-~,-(phenylphosphinidene)dicobaltiron,
D.
64. Stepwise Syntheses of Ruthenium Mixed-Metal Cluster Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Tetraethylammonium Bis(acetonitri1e)tetrachloro-
ruthenate( 1 -), (Et,N)[RuCl,(CH,CN),] . . . . . . . . . . . . . . . . . . . B. Tetraethylammonium Dodecacarbonyltricobaltruthenate
C. (Acetonitrile) dodecacarbonyltricobaltrutheniumcopper,
FeCO,(CO),(PC,H5)S. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Undecacarbonyldicobaltruthenium, RuCo,(CO), . . . . . . . . . .
(1 -), (E~~N)[CO,RU(CO),,] .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CO,R~CU(CH,CN)(CO)~,] ...................................
65. Mixed-Metal Cluster Complexes of Nickel with Ruthenium or with Osmium ........................................................
336
336
339
341 342
343
345 346
347
348
35 1 352 352
353 354
356
356
358
359
360
xxvi Contents
A. Nonacarbonyl(q5-cyclopentadieny1)tri-p-hydrido-
B. Nonacarbonyl(ll’-cyclopentadienyl)tri-p-hydrido-nickel- nickel triosmium, OS~N~(~-H)~(~~-C,H,)(CO)~ . . . . . . . . . . . . .
triruthenium, RU~N~(~-H),(~~-C,H,)(CO),. . . . . . . . . . . . . . . . . .
66. Triosmium and Trinickeltriosmiurn Cluster Complexes. . . . . . . . . . A. Nonacarbonyltris(qS-cyclopentadienyl)-trinickeltriosmium . B. Decacarbonyldihydridotriosmium ............................
67. A. Dicobaltplatinum Complex and Its Platinum Precursor.. . . . . A. Dichloro[ 1,2-ethanediylbis(diphenylphosphine)platinum . . . B. Heptacarbonyl[ 1,2-ethanediylbis(diphenylphosphine)]-
dicobaltplatinum. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
68. Salts of Mixed Platinum-Tetrarhodium Cluster Complexes.. . . . . A. Bis[p-nitrido-bis(triphenylphosphorus)( 1 + )] [tetra-
decacarbonylplatinumtetrarhodate(2 - ), [(Ph,P),N],[PtRh,(CO),,] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Bis[p-nitrido-bis(triphenylphosphorus)( 1 + )] [dodeca- carbonylplatinumtetrarhodate(2 - ), [ (Ph,P),N], [PtRh,(CO), ,I. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
B.
Chapter Six SOLID STATE
69. Synthesis and Crystal Growth of A,[M,X,](A = Cs, Rb; M = Ti, V, Cr; X = C1, Br). . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . A. Single Crystals of A[Cr,X,] .......... .. , ......... , , , ......... B. Synthesis of TiBr, ......... ............... .... ......... ........ C. Polycrystalline A,[Ti,X,] and A,[V,X,]. . . . . . . . . . . . . . . . . . . D. Single Crystals of A3[Ti2X,] and A3[V,X,] . . . . . . . . . . . . . . .
70. Highly Conducting and Superconducting Synthetic Metals.. . . . . A. Synthesis of 5,5‘ , 6,6’-tetrahydr0-2,2’-Bi-l, 3-
dithiolo[4,5-b] [ 1,4]-dithiinylidene, BEDT-TTF 1. 2. 5,5‘ , 6,6-tetrahydr0-2,2’-Bi-l, 3-dithiolo[4,5-b]-
B. Tetrabutylammonium Perrhenate and Superconducting
1,3-Dithiolo[4,5-b]dithiin-2-thione, EDT-DTT, I1 . . . .
dithiinylidene, BEDT-TTF, III . . . . . . . . . . . . . . . . . . . . . . . . . .
Bis(5,5’, 6,6‘-tetrahydrdo-2,2’-bi-l, 3-dithiolo- [4,5-b] [ L4ldithiinylidene)perrhenate.. . . . . . . . . . . . . . . . . . . . . . .
362
363
365 365 367
369 370
370
372
373
375
377 381 382 383 384
386
389
390
39 1
Contents xxvii
C . Tetrabutylammonium fluorosulfate and 2.2’.b i. 1, 3. dithioloC4. 5.61 [ 1. 4ldithiinylidene fluorosulfate ............. 393
Index of Contributors ..................................................... 395 Subject Index .............................................................. 399 Formula Index ............................................................. 411
Chapter One
COMPOUNDS OF THE MAIN GROUP ELEMENTS AND THE LANTHANIDES
1. POTASSIUM TETRADECAHYDRONONABORATE(1- )
Submitted by PATRICK J. DOLAN,* DONALD F. GAINES,’ DAVID C. MOODY,* CATERINA K. NELSON,+ and RILEY SCHAEFFER* Checked by SHELDON G. SHORE’ and STEVEN H. LAWRENCE
There are two synthetically useful routes to salts of the tetradecahydrononaborate( 1 -) ion, [B,H,,] -. The first, which involves the reaction of NaH and pentaborane(9), B,Hg, in tetrahydrofuran (THF) in a 1 :2 molar ratio,’ suffers from two drawbacks:
(1) If a tetraalkylammonium salt is not present, fairly severe contamination by [B, ,Hi,] - salts occurs,’ so the procedure is most useful for preparing tetraalkylammonium salts. The potassium salt is often more desirable as it is the specified precursor in the syntheses of iso-BgH,5,3B,H,,,4 and several metallaboranes.’
*Chemistry Department, Indiana University, Bloomington, IN 47401. +Chemistry Department, University of Wisconsin, Madison, WI 53706. *Department of Chemistry, The Ohio State University, Columbus, OH 43210.
1
2 Compounds of Main Group Elements and Lanthanides
(2) The synthesis employs B,H,, a pyrophoric liquid, and requires special handling procedures.
The second route to salts of the [BgH14]- anion, described below, is accomplished by base degradation of BloH,, (which is a moderately air-stable solid) followed by acid hydrolysis, yielding an aqueous solution of the [B,Hl,]- anion.6 The potassium salt is precipitated by addition of K2C03, and the K[B9H14] is then purified by extraction with diethyl ether.
m Caution. The materials used in this synthesis are toxic and should be handled only in a hood by persons wearing gloves. The diethyl ether extraction must be done with peroxide-free diethyl ether to minimize the possibility of an explosion during the final evacuation.
Procedure
The B1oH14 used in the following procedure should be freshly sublimed at a temperature below 80 "C. Nitrogen should be admitted to the sublimation apparatus only after it has been cooled to room temperature.
A solution of 17 g (0.30 mol) KOH in 100 mL H,O in a 1-L, three-necked flask is stirred in an ice bath under N, until the temperature of the solution reaches 0 "C. Then, 22 g (0.18 mol) of sublimed, freshly powdered BloH14 is added, whereupon the solution rapidly turns yellow. This solution is stirred (at OOC) for - 3 h, by which time most ( - 90%) of the B1oH14 has dissolved.
The solution is slowly acidified to pH2 with 12MHC1, while the temperature is maintained at 0 "C. Much frothing accompanies the acidific- ation. The pH may be monitored using pH paper. The aqueous solution is filtered and then extracted twice with 30-mL portions of hexane to remove any residual decaborane. Then 50 mL of peroxide-free diethyl ether is added to the aqueous solution, followed by 50 g of anhydrous potassium carbonate, K,CO,. The diethyl ether layer is separated, and the aqueous layer is extracted three times with 30-mL portions of ether. The extracts are combined in a 400-mL beaker, which is covered with a watch glass and placed in a vacuum desiccator. The desiccator is evacuated by means of a water aspirator for 4 h, or nearly to dryness. The desiccator is then evacuated for an additional 24 h using a liquid nitrogen trapped two-stage vacuum pump. The desiccator is filled with dry nitrogen and opened. The beaker is transferred to a glove bag for product removal. Yield: 23-26 g (80-90%). The salt may be further purified by dissolving in peroxide-free diethyl ether, whereupon residual salts such as K2C03, KCl, or KOH remain undissolved. After filtration or decantation, evaporation gives a highly purified product. The K[B9H14] is shown to be boron pure by comparison of its "BNMR spectrum with that previously reported.
Potassium Tetradecahydrononaborate( 1 - ) 3
This reaction may also be run on a 10% scale, but the volumes of the hexane and diethyl ether extractions are not reduced. The yield is 90%.
If an alkylammonium salt is desired, it can be obtained by a metathesis reaction. In a typical reaction, 3g of K[B,B,,] is dissolved in 30mL of deoxygenated distilled water, and a solution of 8.8 g of [(C,H,),N]Br in 20 mL of deoxygenated distilled water is added. A precipitate forms immedi- ately. The solution is filtered and the solid is dried by evacuation using a liquid nitrogen trapped two-stage vacuum pump. The product is obtained in 90% yield.
Pro pert ies
Potassium tetradecahydrononaborate( 1 -) is a white solid that is soluble in ethers, water, and acetonitrile. The 86.6 MHz “B NMR spectrum in CD,CN consists of three doublets of equal area: a low-field doublet at - 8.0ppm ( J = 142 Hz) and two high-field doublets at - 20.5 ppm ( J = 132 Hz) and - 23.6 ppm ( J = 142 Hz). The compound K[B,B,,] exhibits no detectable decomposition (via “B NMR) following exposure to air for 1 day. In diethyl ether solution, however, there is significant decomposition after 1 day’s exposure to air.
Salts of the [B9HI4]- anion have been used as the primary source for salts of nido-B,H;,, which in turn are readily oxidized to n-B18H22.5a In metallaborane chemistry salts of the [B9H14]- anion have proved very versatile cluster fragment precursors. Metals ranging from to platinuma have been inserted into [B9H14]- to produce a number of new classes of metallab~ranes.~
References
1. J. B. Leach, M. A. Toft, F. L. Himpsl, and S. G. Shore, J. Am. Chem. SOC., 103,988-989 (1981). 2. P. C. Keller, private communication. 3. J. Dobson, P. C. Keller, and R. Schaeffer, J . Am. Chem. SOC., 87, 3522-3523 (1965). 4. J. Dobson, P. C. Keller, and R. Schaeffer, Inorg. Chem., 7, 399-402 (1968). 5. (a) J. W. Lott and D. F. Gaines, Inorg. Chem., 13,2261-2267 (1974). (b) J. C. Calabrese, M. B.
Fischer, D. F. Gaines, and J. W. Lott, J . Am. Chem. SOC., 96,6318-6323 (1974); (c) D. F. Gaines, C. K. Nelson, and G. A. Steehler, J . Am. Chem. SOC., 106, 7266-7267 (1984).
6. L. E. Benjamin, S. F. Staliej, and E. A. Takacs, J . Am. Chem. SOC., 85, 2674 (1963). 7. P. C. Keller, Inorg. Chem., 9, 75 (1970). 8. A. R. Kane, L. J. Guggenberger, and E. L. Muetterties, J . Am. Chem. S O C . , ~ ~ , 2571-2572(1970). 9. N. N. Greenwood and J. D. Kennedy, in Metal Interactions with Boron Clusters, R. N. Grimes
(ed.), Plenum Press, New York, 1982, pp. 43-1 18.
4 Compounds of Main Group Elements and Lanthanides
2. BROMOTRIMETHYLSILANE
(C,H,),P + Br, + (CH,),SiOSi(CH,), % 2BrSi(CH,), + (C,H,),PO
Submitted by CLAUD10 PALOMO* and JESUS M. AIZPURUA* Checked by JOYCE Y. COREY' and JANET BRADDOCK'
The methods for the preparation of bromotrimethylsilane include the treatment of hexamethyldisiloxane with bromine reagents such as phosphorus tribromide,'*2 2,2,2-tribromo-l,3,2 i5-benzodioxaphosphole (catechyl phos- phorus tribromide),2 and aluminium tribromide,, the yields being in the range from 73 to 87%. A further method4 shows that bromotrimethylsilane can be obtained from aminosilanes and hydrobromic acid, but the yield (55%) is lower than in the former methods. Other methods involve the use of expensive reagents, such as hexamethyldisilane, 1,4-bis(trimethylsily1)-2,5- cyclohexadiene, and 1,4-dihydro- 1, 4-bi~(trimethylsilyl)naphthalene.~ Finally, some alternative procedures have been developed for its in situ preparati~n.~
The following procedure is an operatively simple route for the synthesis of bromotrimethylsilane on a preparative laboratory scale from reagents that are readily accessible and inexpensive. This could be a method of choice in some laboratories despite the fact that bromotrimethylsilane is now commercially available (Petrach Systems, Aldrich, or Alpha). Moreover, the procedure also serves as a suitable method for the synthesis of azidotrimethylsilane and isocyanatotrimethylsilane, and is specially useful for the preparation of cyanotrimethylsilane. Thus a mixture of triphenylphosphine dibromide, hexamethyldisiloxane, and a catalytic amount of powdered metal zinc in 1,2- dichlorobenzene is heated under reflux to produce bromotrimethylsilane in nearly quantitative yield, which is simultaneously distilled over a suspension of the corresponding pseudohalogenoacid salt in N , N-dimethylformamide as solvent.6
Procedure . Caution. Owing to the lachrymatory properties of bromine reagent and halosilane product, this reaction should be carried out in a well-ventilated hood.
*Department to Organic Chemistry, University of Euskal Herria, Donostia, Apdo 1072, 20080 Spain. 'Department of Chemistry, University of Missouri, St. Louis, MO 63121.
Bromotrimethylsilane 5
Source of Reagents
Triphenylphosphine was obtained from BASF, and the freshly opened material was used without further purification or drying. 1,2- Dichlorobenzene from Panreac, was used without purification or drying. These materials were obtained from Aldrich by the Checkers. Hexamethyl- disiloxane was obtained from hydrolysis of chorotrimethylsilane and distilled before use. Thus, a mixture of chlorotrimethylsilane (253 mL, 2.00 mol), ice (1 50 g), and water (200 mL) was vigorously stirred for 2 h, and then, the inorganic layer was separated using a separatory funnel. The organic layer was successively washed with water (50 mL), 2 N sodium hydroxide (100mL), and water again (50mL), after which, the crude siloxane was dried over MgSO, and purified by distillation to afford pure hexamethyldisiloxane (314.8 g, 97%)(bp 101-102 "C) and (bp 102 "C).' The chlorotrimethylsilane was obtained from Wacker-Chemie in Germany, or may be obtained from Petrach Systems, Aldrich, or Alpha in the United States.
In a dry 250-mL round-bottomed flask fitted with a magnetic stirring bar and a funnel equipped with a drying tube are placed (39.2g, 0.15mol) of triphenylphosphine and 75 mL of 1,2-dichlorobenzene. After this, 16.8 g (22 mL, 0.104 mol) of hexamethyldisiloxane and a catalytic amount (0.5 g) of powdered zinc metal are added to this stirred mixture and the flask is cooled in an ice bath. Bromine 27.2g (8.71 mL, 0.17mol), dissolved in 25mL of 1,2- dichlorobenzene is placed in the addition funnel and added dropwise to the mixture over a 20 to 30-min period. During the addition, the colorless or yellow suspension becomes bright yellow. It is very important to achieve yellow coloration of the mixture. An excess of bromine may be used for this purpose. This fact is critical for a good yield and purity of the product. After the addition is completed, the cooling bath is removed and the reaction flask is placed in a silicone oil bath.
Caution. Due to temperatures reaching 200-215 "C, a silicone oil bath is to be used. Ordinary hydrocarbon oil baths will ignite at these temperatures.
Under an atmosphere of dry nitrogen gas, the dropping funnel is replaced by a fractional distillation apparatus provided with a 10-cm Vigreux column and a 5-cm water-cooled condenser. The system is heat-dried under a flow of nitrogen gas with an electric heat gun or may be assembled from oven-dried glassware. The mixture is then heated over a period of 20-30min until the silicone oil bath reaches 130-140°C. During this time, the initial yellow precipitate is partially dissolved and the mixture refluxes smoothly. The silicone oil bath is maintained at this temperature for an additional 30min. Heating is then increased over the period of 1 h to achieve distillation of the product; the final oil temperature reaches 200 to 215 "C.
The yield of bromotrimethylsilane is 30.60 g (96%, based on hexa- methyldisiloxane used) (bp 80-8 1 "C). Other characteristic^,^ (bp 79.9 "(7754
6 Compounds of Main Group Elemenrs and Lanthanides
torr, d:': 1.188. Bromotrimethylsilane hydrolyzes more rapidly than chlorotrimethylsilane. The purity of the product is 98% as established by NMR in CCl, solution. A single peak at 0.5 ppm downfield from tetramethyl- silane is observed, the only impurities being siloxane hydrolysis products.
Properties
Bromotrimethylsilane has proven to be useful for a wide variety of applic- ations most of them being Other recent applications are mild cleavage of oxiranes,' the synthesis of glycosyl bromides," the selective cleavage of tetrahydro-2,5-dimethoxyfuran and tetrahydro-2,6-dimethoxy- pyran," the cleavage of esters and ethers,I2 and the synthesis of benzyl bromides.
References
1. W. F. Gilliam, R. N. Meals, and R. 0. Sauer, J. Am. Chem. SOC., 68, 1161 (1948). 2. H. Gross, C. Bock, B. Costisella, and J. J. Gloede, Prakt. Chem., 320, 344 (1978). 3. M. G. Voronkov, B. N. Dolgov, and N. A. Dimitrieva, Proc. Acad. Sci. USSR, 84,959 (1952). 4. D. L. Bailey, L. H. Sommer, and F. C. Withmore, J. Am. Chem. SOC., 70,435 (1948). 5. A. H. Schmidt, Aldrichimica Acta, 14, 31 (1981) and references cited therein. 6. J. M. Aizpurua and C. Palomo, Noun J . Chim., 8, 51 (1984). 7. A. E. Pierce, Silylation of Organic Compounds, Pierce Chemical Co., Rockford, 111 (1968). 8. E. Colvin, Silicon in Organic Synthesis, Butterworths, London, 1981, p. 288. 9. H. R. Kricheldorf, G. Morber, and W. Regel, Synthesis, 383 (1981).
10. J. W. Gillard and M. Israel, Tetrahedron Lett., 24, 513 (1981). 11. T. H. Chan and S. D. Lee, Tetrahedron Lett., 24, 1225 (1983). 12. E. C. Friedrich and G. Delucca, J. Org. Chem., 48, 1678 (1983). 13. C. Palomo and J. M. Aizpurua, Tetrahedron Lett, 25, 1103 (1984).
