Inorganic Syntheses, Volume 17

263 Pages·1977·17.944 MB·English

INORGANIC
SYNTHESES
Volume XVII
.................... .............................................
Board of Directors
W. CONARD FERNELIUS Kent State University
WILLIAM L. JOLLY University of California
HENRY F. HOLTZCLAW Unicersit!. of Nebraska
JAY H. WORRELL University of South Florida
FRED BASOLO Northwestern University
JOHN K. RUFF University of Georgia
AARON WOLD Brown University
GEORGE W. PARSHALL E. I. du Pont de Nemours
& Company
Future Volumes
XVIII Bodie E. Douglas
XIX Duward F. Shriver
XX Daryle H. Busch
International Associates
E. 0. FISCHER Technische Hochschule (Munich)
JACK LEWIS Cambridge University
LAMBERTO MALATESTA University of Milan
F. G. A. STONE Bristol Uniuersity
GEOFFREY WILKINSON Imperial College of Science
and Technology (London)
AKIO YAMAMOTO Tokyo Institute of Technology
Editor-in-Chief
ALAN G. MacDIARMID
Department of Chemistry
University of Pennsylvania
Philadelphia, Pennsylvania
~.W.H.H...................~......~~H
INORGANIC
SYNTHESES
Volume XVII
McGRAW-HILL BOOK COMPANY
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INORGANIC SYNTHESES, VOLUME XVII
Copyright 0 1977 by McGraw-Hill, Inc. All rights reserved.
Printed in the United States of America. No part of this
publication may be reproduced, stored in a retrieval system,
or transmitted, in any form or by any means, electronic,
mechanical, photocopying, recording, or otherwise, without
the prior written permission of the publisher. Library of
Congress Catalog Card Number 39-23015
ISBN 0-07-044327-0
1234567890 KPKP 786543210987
CONTENTS
P refice .............................................................................................. ix
Notice to Contributors ............................................................................. x
Chapter One METAL HYDRIDES 1
I . MAING ROUPH YDRIDE(SE . C . Ashby) . . .................................... 1
1. Magnesium Dihydride ................................................. .......2
2. Zinc Dihydride ............................................................................... 6
3 . Lithium Trihydridozincate( 1- ) and Lithium Tetrahydridozincate(2 - ) .................9.
A. Lithium Trihydridozincate( 1- ) .... ........................ .to
B. Lithium Tetrahydridozincate(2 - ) ......................................
4. Sodium Trihydridodimethyldizincate(1 - ) and Sodium Trihydridozincate( 1-
A . Sodium Trihydridodimethyldizincate(1 - ) ........................................ 14
B. Sodium Trihydridozincate( 1 - ) ................... .................
5 . Calcium Bis[tetrahydroborate( 1 - )] .......................................
6. Quaternary Ammonium and Phosphonium Heptahydroborates .............
A. Methyltriphenylphosphonium Tetrahydroborate(1 - ) ............................... 22
B. Tetrabutylammonium Tetrahydroborate(1 - ) .......................................... 23
C. Methyltriphenylphosphonium Heptahydrodiborate(I - ) .... ..................... 24
D. Tetrabutylammonium Heptahydrodiborate(1 - ) ...............................
7. Potassium Tri(sec-butyl)hydroborate(l - ) ........................................... 26
8. Bis(dimeth y1amino)borane ............................................................ 30
9. Bis-pc-(dimethyIamino)-diborane(6). ................................................. 32
10. p-(Dimethylamino)-diborane(6) .......... ....................................... 34
11. Trihydrido(trimeth y1amink)aluminum and (Diethy1amino)hydridoaluminum
Complexes ............................................................................. 36
A . Triliydrido(trimethylamine)aluminum ............................................ 37
B . (Diethylamino)dihydridoaluminum ................................................ 40
C. Bis(diethylarnino)hydridoaluminum .............................................. 41
12. Trihydrido(trimethylarnine)galliurn .................................................. 42
13. Lithium Tetrahydridogallate(1- ) ................................................... 45
14. Sodium and Potassium Tetrahydridogallate( 1- ) ...................................... 48
I1. TRANSITIOMNE TALH YDRIDCE OMPLEXE(HSe rbert D . Kaesz) ..................... 52
15 . Hydrido Phosphine Arene Complexes of Molybdenum ............................... 54
A . Bis(16-benzene)molybdenum ..................................................... 54
B . (rl6-Benzene)dihydridobis(triphenylphosphine)molybdenum. ...................... 57
C . (16-Benzene)tris(dimethylphenyIphosphine)hydridomolybdenum
Hexafluorophosphate( 1- ) .............................................................. 58
D . (~6-Benzene)tris(dimethylphenylphosphine)dihydridomolybdenum
Bis[hexafluorophosphate(l - )] ................................................... 60
16. Bis[ethylenebis(diphenylphosphine)]hydrido(2. 4-pentanedionato)molybdenum(II) ....6 1
17. Tris(dimethylphenylphospliine)pentahydridorhenium(V) ............................. 64
18. Dodecacarbonyltri-p-hydrido-triarigulo-trirhenium(1.). ............................... 66
19. Bis[ethylenebis(diphenylphosphine)]hydridoiron Complexes .......................... 69
A . Chlorobis[ethylenebis(diphenylphosphine)]hydridoiron(Il) ........................ 69
B . Bis[ethylenebis(diphenylphosphine)]hydridoiron(II) Tetraphenylborate( 1- ) .......7 0
C . Bis[ethylenebis(diphenylphosphine)]hydridoiron(I) ............................... 71
V
vi Contents
20 . Hydridonitrosyltris(triphenylphosphine)ruthenium(I) ................................ 73
21. Dihydridotetrakis(triphenylphosphine)ruthenium(II) ................................. 75
22 . Hydrido[(~6-phenyl)diphenylpliospliine]bis(triphenylphosphine)ruthenium(II)
Tetrafluoroborate( 1 - ) ............................................................
23 . (Acetato)hydridotris(triphenylphosphine)ruthenium(II) ............................... 79
+
24 . Hydridobis[( )-dioplrhodium(1) .................................................... 81
25 . Nickel and Palladium Chlorohydridobis(phosphine) Complexes ...................... 83
A . trans-[Chlorohydridobis(tricyclohexylphosphine)nickel] ........................... 84
B . trans-[Chlorohydridobis(triisopropylphosphine)nickel]. ........................... 86
C. trans-[Chlorohydridobis(tricyclohexylphosphine)palladium] ....................... 87
26 . Hydrido[tetrahydroborato(l - )] Nickel and Palladium Complexes ..................... 88
A . trans-[Hydrido[tetrahydroborato( 1- )~bis(tricyclohexylphosphine)nickel]. .........8 9
B . trans-[Hydrido[tetrahydroborato(l - )]bis(tricyclohexylphosphine)palladium] ......9 0
27 . Bis(~5-cyclopentadienyl)[tetrahydroborato1( - )]titanium ............................. 91
Chapter Two CARBONYL . PHOSPHINE. OLEFIN. AND
RELATED TRANSITION METAL
COMPLEXES 95
28 . (Carbene)pentacarbonyl Complexes of Chromium and Tungsten ...................... 95
A . Pentacarbonyl(methoxymethylcarbene)chromium(O) .............................. 96
B . Pentacarbonyl(methoxymethylcarbene)tungsten(O) ............................... 97
C. Pentacarbonyl[ 1 - (pheny1thio)ethy lidene]chromium(O) .............................. 98
D. Pentacarbonyl[l - (phenylthio)ethylidene]tungsten+(O ) ............................. 99
29 . Dicarbonyl(~’-cyclopentadienyl)(thiocarbonyl)iron(1 ) Hexafluorophosphate( 1 - )
and Dicarbony1(~*-cyclopentadienyl)[(methylthio)thiocarbonyl]iron ................1. 00
30 . Tricarbonyl(q5-cyclopentadienyl)silylC omplexes of Chromium, Molybdenum,a nd
Tungsten .......................................................................... 104
31. Phosphine Complexes of Rhenium ................................................. 110
A . Trichlorooxobis(triphenylphosphine)rhenium(V) .................................. 110
B . mer-Trichlorotris(dimethylphenylphosphine)rhenium(III) ........................ 111
32 . n-Cycloocten yl-n- 1,5 -cyclooctadienecobalt ......................................... -112
33 . Dodecacarbonyltetrarhodium ...................................................... 115
34 . Olefin, Acetylene, Phosphine,I socyanide,a nd Diazene Complexes of Nickel(0) .......1 17
A . Tetrakis(t-butyl isocyanide)nickel(O) ............................................ 118
B . Tetrakis(triphenylphosphine)nickel(O) ............................................ 120
C. (Azobenzene)bis(t-butyl isocyanide)nickel(O) .................................... 122
35 . (Carboxylato)(triphenylphosphine) Complexes of the Platinum Metals ............... 124
A . Bis(acetato)dicarbonylbis(triphenylphosphine)ruthenium(II) ..................... 126
B . (Acetato)carbonylchlorobis(triphenylphosphine)ruthenium(II) ................... 126
C. (Acetato)carbonylhydridobis(triphenylphosphine)ruthenium(II) ..................1 26
t) . Carbonylbis(trifluoroacetato)bis(triphenylphosphine)ruthenium(II). .............1 27
E . Nitrosyltris(trifluoroacetato)bis(triphenylphosphine)ruthenium(II) .................1 27
F . Carbonylchloro(trifluoroacetato)tris(triphenylphosphine)osmium(II) ..............1 28
G . Carbonylbis(trifluoroacetato)bis(triphenylphosphine)osmium(II). ................1 28
H. (Acetato)tris(triphenylphosphine)rhodium(I) .................................... 129
1. Bis(acetato)nitrosylbis(triphenylphosphine)rhodium(III) ......................... 129
J . (Acetato)dihydridotris(triphenylphosphine)iridium(III) .......................... 129
K . cis-[Bis(acetato)bis(triphenylphosphine)platinum(II)] ........................... 130
3 6. trans-~Chloroethylbis(triethylphosphine)platinum(II)]. .............................. 132
37 . Tetrakis(t-butyl isocyanide)di-p-chloro-dipalladium(1).. ................................ 134
Contents vii
Chapter Three OTHER TRANSITION METAL
COMPOUNDS I 39
38 Iron(I1) and Cobalt(II1) Clathrochelates Derived from Dioximes ....................... 139
A . [[Tris.[p.[(2, 3.butanedione dioximato)-0 : O']]difluorodiborato)(2 - )]-
N. N'. N". N"'. N". N'""]cobalt(III) Tetrafluoroborate( I -) ......................... 140
B . [[Tris.[p.[(2. 3.butanedione dioximato)-0 : 0'11 difluorodiborato(2 - )]-
N. N. N". N"'. N"". N""']iron(II) ............................. ...............1 42
C. [[Tris-[p-[( 1. 2.cyclohexanedione ximato)-0 : O']]d ifluorodi
N. N'. N .N "'. N"". N""']iron(II) ................................................ 143
D . [[Tris-[p-[( 1, 2.cyclohexanedione dioximato)-0 : 0.11 dihydroxydiborato(2 - )]-
N. N,N ". N"'. N"". N""']iron(IIj ....................................................... 144
E . [[Tris.[p.[(2, 3.butanedione diox
N, N. N .N "'. N'.... N""']iron(II)
F . [[Tris-[p-[( 1.2diphenyl.l. 2.etha
N, N ,N ". N"', N"". N""']iron(II) ...........................
39 Potassium cis-[Diaquabis(oxalato)chromate(III)] Dihydrate and Potassium
frans-[Diaquabis(oxalato)chromate(III)]T rihydrate ................................. 147
A . Potassium cis-[Diaquabis(oxalato)chromate(lII)] Dihydrate ...................... 148
B . Potassium trans-[Diaq.u abis(oxalato)chromate(III)] Trihydrate ...................1 49
40 . Cobalt(II1). Rhodium(II1) and Iridium(lI1) Carbonato Complexes of the
Pentaammine Type ................................................................ 152
41 . Technetium(VI1) Oxide ............................................................ 155
Chapter. Four. MAIN GROUP COMPOUNDS 159
42 . Tris(dialky1amino)boranes. ........................................................ 159
A . Tris(diethy1amino)borane ........................................................ 159
B . Tris[(l-methylpropyl)amino]borane ............................................... 160
43 . Tris(N-methylani1ino)borane ....................................................... 162
44 . 1,3-Diaza-2 .boracycloalkanes ...................................................... 164
A . 1,3.Dimethyl.1,3.diaza. 2.boracyclopentane ...................................... 165
B. 1,3.Dimethyl.1,3.diaza. 2.boracyclohexane ...................................... 166
45. Gallium Trichloride ............................................................... 167
46. Cyclopentadienylsilane and (Methylcyc1opentadienyl)silane .......................... 172
A . Cyclopentadienylsilane ......................................................... 172
B . (Methylcyclopentadieny1)silane. ................................................ 174
47 . Cyclopen tadienylgermane .......................................................... 176
48 . Cyclopentadienyltrimethylstannane ................................................ 178
49. Bis(trimethy1tin) Oxide ............................................................ 181
50. Methyldiphenylphosphine Oxide and Dimethylphenylphosphine Oxide ..............1 83
A . Methyldiphenylphosphine Oxide .............................................
B . Dimethylphenylphosphine Oxide ............................................... 185
51. Lithium Diphenylphosphide and Diphenyl(trimethylsily1)phosphine .......... : ......1 86
A . Lithium Diphenylphosphide .................................................... 186
B . Dip.hen.yl(.trim ethy.1si.lyl.)p.hos.ph ine .............................................. 187
52 . Pentathiazyl, [S,N,]+. Salts ......................................................... 188
A . Pentathiazyl Tetrachloroferrate( 1 - ) and Pentathiazyl
Tetrachloroaluminate( 1- ) ..................................................... 190
B. Pentathiazyl Hexachloroantimonate(1- ) ....................................... 191
53. Importance of Excess Base in the Synthesis of Sodium Monothiophosphate ..........1 93
Correction ............................................................................. 195
viii Contents
Appendix
Cautionary Note Concerning the Storing and Handling of Tetrasulfur
Tetranitride. S4N. ......................................................................... 197
Inder of’ Contributors ................................................................... 201
Subject Index ........................................................................... 205
Formula Index .......................................................................... 217
PREFACE
The format used in this volume follows the organizational pattern used in
recent volumes. An attempt is made to group syntheses in different chapters
in accordance with specific areas of interest. Chapter One, which describes
compounds containing metal-hydrogen bonds, is divided into two parts:
main group hydrides and transition metal hydride complexes. For conveni-
ence, transition metal compounds not containing a metal-hydrogen bond
are treated separately. Those compounds containing only carbonyl, phos-
phine, olefin, and similar types of ligands are grouped together in Chapter
Two; all other types of transition metal compounds are described in Chapter
Three. Chapter Four contains all compounds of the main group elements
with the exception of the metal hydrides which are, as noted above,
described in Section I of Chapter One.
Inorganic Syntheses, Inc., is a nonprofit organization dedicated to the
selection and presentation of tested procedures for the preparation of com-
pounds of more than routine interest. The Editorial Board seeks the
cooperation of the entire scientific community in realizing these goals. The
editor for Volume XVIII is B. E. Douglas; for Volume XIX, D. F. Shriver;
and for Volume XX, D. H. Busch Directions for submitting preparations
follow this preface.
I am particularly indebted to the many scientists who have willingly con-
tributed their time and materials to checking the syntheses and to the
authors for collaborating with the checkers where appropriate, in changing
their manuscripts for greater clarity.
Finally, I wish to thank those members of Inorganic Syntheses, Inc.,
who read the original manuscripts and gave me much valuable advice and
help. I am especially indebted to Professors Eugene C. Ashby and Herbert
D. Kaesz who contacted prospective authors for the syntheses of main
group hydrides and transition metal hydrides, respectively. I also wish to
thank Warren H. Powell and Mr. Thomas E. Sloan for their invaluable
assistance in nomenclature matters and in the copy-editing of the
manuscripts as well as Professor W. Conard Fernelius for his meticulous
reading of proof for the entire volume.
Alan G. MacDiarmid
ix
NOTICE TO CONTRIBUTORS
The INORGANIC 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
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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. An ideal synthesis is one which presents a
new or revised experimental procedure applicable to a variety of related
compounds, at least one of which is critically important in current research.
However, syntheses of individual compounds that are of interest or impor-
tance are also acceptable.
The Editorial Board lists the following criteria of content for submitted
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INORGANIC SYNTHESES. The Introduction 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 are associated with the procedure.
The Procedure should present detailed and unambiguous laboratory
directions and be written so that it anticipates possible mistakes and mis-
understandings on the part of the person who attempts to duplicate the
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and solvents should be stated. The scale should be reasonable for normal
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either up or down should be discussed. The criteria for judging the purity
xi