Inorganic Syntheses, Vol. 15

324 Pages·1974·17.632 MB·English

by  George W. Parshall (ed.)

INORGANIC
SYNTHESES
Volume XV
Board of Directors
THERALD MOELLER Arizona Srare Unirersit).
WILLIAM L. JOLLY University of California
HENRY F. HOLTZCLAW Universir? of Nebraska
STANLEY KIRSCHNER Wayne Srate Unirersitj
F. A. COTTON Texas A & M Unirersitji
JOHN K. RUFF U/iirersiry of Georgia
AARON WOLD Brown Universirv
Future Volumes
XVI Fred Basolo
XVII Alan G. Mac Diarmid
XVIII Bodie Douglas
International Associates
E. 0. FISCHER Technische Hochschule I Munich)
JACK LEWIS Cambridge University (London)
LAMBERTO MALATESTA Unirersiry of Milan
GEOFFREY WILKINSON Imperial College of Science
and Technology (London)
Editor -in -Chief
GEORGE W. PARSHALL
Central Research Department
......................
E. I. du Pont de Nemours & Company
Wilrnington, Delaware
....................
INORGANIC
SYNTHESES
Volume XV
McGRAW-HILL BOOK COMPANY
,Vew York St. Louis San Francisco Diisseldorf Johannesburg
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INORGANIC SYNTHESES, VOLUME XV
Copyright 0 1974 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
0-07-048521-6
1234567890 KPKP 7987654
To Ronald S. Nyholm
1917-1971
CONTENTS
Preface ................ ......................... ...... x.i. .
Notice to Contributors ... .......................... ...... xu1
Chapter One METAL COMPLEXES OF OLEFINS
1. Bis(l.3.5. 7.~yclooctatetraene)iron(O). ........................................
2 . Bis( 1. 5.cyclooctadiene)nickel(O~ .............................................
3 . Ethylenebis(tri-o-tolylp hosphite)nickel(O) and Tris(tri-o-tolylp hosphite)-
nickel(0) ................................................. .... 9
A . Ethylenebis(tri-o-tolylp hosphite)nickel(O) ............................... 10
B . Tris(tri-o-tolyl phosphite)nickel(O) ....................................... 11
C . Tris(tri-o-tolyl phosphite)nickel(O) ....................................... 12
4. Di-p-chlorotetrakis(ethylene)dirhodium(I)2,, 4-Pentanedionatobis(ethylene)-
rhodium(]), and Di-p-chlorotetracarbonyldirhodium(1.). ....................... 14
A . Di-p-chlorotetrakis(ethylene)dirhodium(I). .............................. 14
B . 2. 4-Pentanedionatobis(ethylene)rhodium(l) ............................... 16
C . Di-p-chlorotetracarbonyldirhodium(1). .................................. 17
5 . Cyclooctene and 1,5 -Cyclooctadiene Complexes of Iridium(]) ................... 18
A . Di-p-chloro-bis(l,5-cyclooctadiene)diiridium(.I.). .................... 18
B . Di-p-chlorotetrakis(cyclooctene)diiridium(I.). ........................... 19
Chapter Two METAL COMPLEXES OF DINITROGEN
AND OF HYDROGEN ......................... 21
6 . trans-(Dinitrogen)bis[ethylenebis(diethylphosphine~]hydridoiron(I~)
Tetraphenylborate ........................ .............. ........ 21
A . trans-Dichlorobis[ethylenebis(diethylphosp (11) .......... ......... 22
B . truns-Chlorobis[ethylenebis(diethylphosphine)]hydridoiron(~~.). .... ........ 23
C. rrans-(Dinitrogen)bis[ethylenebis(diethylphosphine)]hydridoiron(I~)
Tetraphenylb orate ......... ......................... ......... 24
7 . trans-Bis(dinitrogen)bis[ethyleneb Iphosphine)]mol ybdenum(0) ......... 25
8 . (p.Dinitrogen-N,N ')bis[bis(tricyclohexylphosphine)nickel(O)] ........... ........ 29
A . (Ethylene)bis(tricyclohexylphosphine)nickel ..................... ......... 29
B . (p.Dinitrogen.N, N')bis[bis(tricyclohexylphosphine)nickel(O)] ....... ........ 30
9 . Dinitrogen and Hydrogen Complexes of Ruthenium .......... 31
A . Dinitrogendihydridotris(triphenylphosphine)ruthenium(Il) ......... 32
B . Tetrahydridotris(triphenylphosphine)ruthenium(IV) ...... 33
...
viii Contents
10 . Pentahydridobis(trimethylphosphine)iridium(V) ......................... 34
A . Trimethylphosphonium Tetrachlorobis(trimethylphosphine)iridate(l - )
and Trichlorotris(trimethylphosphine)iridium(III) .................... ..... 35
B . Pentahydridobis(trimethylphosphine)iridium(V). ..................... ..... 36
1 1. Hydride Complexes of Iron(I1) and Ruthenium(I1) ....................... ..... 38
A . Bis[ethylenebis(diphenylphosphine)]dihydridoiron(II) ................ ..... 39
B . Tetrakis(triethy1 phosphite)dihydridoruthenium(II) ................... ..... 40
12 . Tetrahydridotetrakis(methyldiphenylphosphine)molybdenum(lV) .......... ..... 42
A . Tetrachlorobis(methyIdiphenylphosphine)molybdenum(IV) ............ ..... 43
B . Tetrahydridotetrakis(methyldiphenylphosphine)molybdenum(IV) ....... ..... 43
Chapter Three TRIPHENYLPHOSPHINE COMPLEXES OF
TRANSITION METALS ........................ 45
13. Complexes of Ruthenium. Osmium. Rhodium. and Iridium Containing
Hydride. Carbonyl. or Nitrosyl Ligands ............................... 45
A . Carbonylchlorohydridotris(triphenylphosphine)ruthenium(lI) ........ 48
B. Carbonyldihydridotris( triphenyIphosphine)ruthenium(II)( WhiteI somer) 48
C. Tricarbonylbis(triphenylphosphine)ruthenium(O). ................... 50
D . Trichloronitrosylbis(triphenylphosphine)ruthenium(II). .............. 51
E . Dinitrosylbis(tripheny1phosphine)ruthenium ........................ 52
F . Carbonylchlorohydridotris(triphenylphosphine)osmium(Il). .......... 53
G . Carbonyldihydridotris(triphenylphosphine)osmium(II). .............. 54
H . Dicarbonyldihydridobis(triphenylphosphine)osmium(II) . . 55
1 . Tetrahydridotris(triphenylphosphine)osmium(lV.). ...... 56
J . Trichloronitrosylbis(triphenylphosphine)osmium(II) ..... 57
K . Hydridotetrakis(triphenylphosphine)rhodium(I) 58
L . Carbonylhydridotris(tripheny1phosphine)rhodiu 59
M . Dichloron~trosylbis(tr~phenylphosphine)rhodium(I.). .... 60
N . Nitrosyltris(tripheny1phosphine)rhodium. .............. 61
0. Dichloronitrosylbis(triphenylphosphine)iridium(I) . . 62
14 . Fluoro Complexes of Rhodium(1) and Iridium(1) ............ 64
A . rrans-Carbonylfluorobis(triphenylphosphine)rhodium(I). ................... 65
B . tr.ans-Carbonylfluorobis(triphenylphosphine)iridium(l). .................... 67
15 . Covalent Perchlorato Complexes of Iridium and Rhodium ..................... 68
A . rra,I s-Carbonylperchloratobis(triphenylphosphine)iridium(. ................ 69
B . rrnris-Carbonylperchloratobis(triphenylphosphine)rhodium(I) ............... 71
16 . tra,i s-Carbonyl(cyanotrihydridoborato)bis(triphenylphosphine)rhodium(I). ....... 72
Chapter Four OTHER TRANSITION-METAL
COMPOUNDS .................................... 75
17. x-Ally1 Complexes of Palladium and Platinum .......................... 75
A . Di-p-chloro-bis[(1-ethyl-2-methyl-n-allyl)palladium.]. ............... 77
B . Di-p-chloro-bis~[1-(hydroxyethyl)-3-methyl-~-allyl]palladi.u.m.~. .... 78
C. Tetrakis[allylchloroplatinum(II)] ................................. 19
18. Dicarbonylchloro(p-toluidine)iridium(I). ......................... 82
+
19 . p-Nitrido-bis(tripheny1phosphorus)( 1 ) (
Carbonyl Anions .................................................. . 84
A . p-Nitrido-bis(tripheny1phosphorus)( 1 + ) Chloride . . 85
B . p-Nitrido-bis(tripheny1phosphorus)( 1 + ) Nitrate . . . 87
C . p-Nitrido-bis(triphenylph0sphorus()I +)T etracarb . 87
D . p-Nitrido-bis(tripheny1phosphorus)( 1+ ) Salts of
[MZ(CO),,]2 -(M = Cr,M o, W). ............ 88
Contents 1x
+
20 . Dicarbonyl-k5-cyclopentadienylnitrosylmanganes(e1 )
Hexafluorophosphate (I -) ......... ............... .. 91
21 . Hexaammineplatinum(1V) Chloride . . .. 93
A. Dichlorotetrakis(methylamine)platinum e .................... .. 93
B. Hexaammineplatinum(1V) Chloride ................ .. 94
22 . Bis(l,l,l,5.5.5-hexafluoro-2.4-pentanedionato)nickel(II)an d-cobaIt(I1) .. 96
23. Ammonium Pentahalooxomolybdates(2 - ) ................................. .. 100
A . Ammonium Pentachlorooxomolybdate(2-) ............................ .. 101
B . Ammonium Pentabromooxomolybdate(2-) ............................ .. 102
24 . 13-Vanadomanganate(lV)a nd Nickela .. 1 u3
A . Potassium Vanadate(V) ........ .. 104
B. Potassium 13-Vanadomanganate(I ................ .. 105
C . Reduced Potassium 13-Vanadoma .. 106
D. Ammonium 13-Vanadomanganate ydrate ......... .. 107
E . Potassium 13-Vanadonickelate(lV) 16-Hydrate .................. .. 108
ChapterFiue BORON COMPOUNDS ............ .. 111
I-)
25 . Octahydrotriborate(1- ) ([B.H, Salts .. 111
26 . Pentaborane(9) (B.H. ) .............. .. 118
27 . Dimethylamine-Borane ............. ................... .. 122
28 . Dimethylamine-Tribromoborane .............................. .. 125
29 . Methyldiphenylphosphine-Borane and Dimethylphenylphosphine-Borane ....... . 128
A . Methyldiphenylphosphine-Bo .. I28
B. Dimethylphenylphosphine-Borane 132
30. Triphenylborane ............................................... 134
31 . Sodium Triethylhydroborate. Sodium Tetraethylborate.
and Sodium Triethyi-I-propynylborate. ................................... 136
A. Sodium Triethylhydroborate ......................................... 137
B. Sodium Tetraethylborate ............................................ 138
C . Sodium Triethyl-I-propynylborate .................................... 139
32 . Tetraalkyldiboranes and 9-Borabicyclo[3.3.1] nonane Dimer ................. 141
A . “Tetraethyldiborane” and “Tetrapropyldiborane” ....................... 142
B. 9-Borabicyclo[3.3.1]nonane Dimer .................................... 147
33 . Chlorodiethylborane and Chlorodiphenylborane ........................... 149
A. Chlorodiethylborane ................................................ 151
B. Chlorodiphenylborane .............................................. 152
Chapter Six GERMANIUM HYDRIDE DERIVATIVES .... 155
34. Bromogermane and Dibromogermane ..................................... .. 157
35. Chlorogermaneand lodogermane ........................................ .. 161
A . Chlorogermane .................................................... .. 161
B . lodogermane ...................................................... .. 163
36 . Fluorogermane and Digermylcarbodiimide ... ......................... 164
A . Fluorogermane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 65
B. Digermylcarbodiimide ................. ......................... 166
37. lododigermane and Methyldigermane ........ ......................... 169
A . Iododigerrnane ........................ ......................... 170
B. Methyldigermane ..................... ......................... 172
38. Pentacarbonylgermylmanganese ............. ......................... 174
39 . Germylphosphiae ......................... ......................... Ill
40. Digermyl Sulfide(Digermt hiane) ............. ......................... 182
x Contents
Chapter Seven PHOSPHORUS COMPOUNDS . .
41. Ethylenebis(dimethy1phosphine) [ 1,2-bis(Dimethylphosphino)ethane],
Tetramethyldiphosphane Disulfide, and Tetramethyldiphosphane . . . . . . . . . . . . . . . 185
A. Tetramethyldiphosphane Disulfide . . . . . . . . . . . . . . . . . . . . . . . . . . 186
B. Tetramethyldiphosphane . . . . . . . . . . . . . . . . . . . . . . 187
C. Ethylenebis(dimet . . . . . . . , . . . . . . . . . . . . . 188
42. Dimethylphosphinothioic Chloride and Dimet us Chloride . . . . . . . . . . 191
A. Dimethylphosphin . . . , , . . . . . . . . . . . . 192
B. Dimethylphosphin __...___.___...._.1.9.2. .....
43. Phosphoric Trihalides .......................... 194
A. Phosphoric Chlori . .. . .. . .. .. .. . .. .. .. .. .... 195
B. Phosphoric Dichloride Fluoride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
C. Phosphoric Bromide Diiluoride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
44. p-Nitrido-bis[amidodiphenylphosphorus]( 1 +) Chloride . . . . . . . . . . . . . . . . . . . . . . . 199
Chapter Eight MAIN GROUP AND ACTINIDE
COMPOUNDS .................................. 203
45. Trimethylgallium _...__.._._.. ........................................ 203
46. Hexamethyldisilthiane and Hexamethylcyclotrisilthiane . . . . . . . . . . . . . . . . . . . . . . . 207
A. Hexamethyldisilthiane via 1-(Trimethy1silyl)imidazole. . . . . . . . . . . . . . . . .
B. Hexamethyldisilthiane via Chlorotrimethylsilane . . . . . . . . . . . . . . . . . . . . .
C. Hexamethylcyclotrisilthiane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
47. Polyatomic Cations of Sulfur, Selenium, and Tellurium . . . . . . . . . . . . . . . . . . . . . . . . 213
A. Octasulfur p-FIuorobis(pentafluoroantimonate(V)
and Octasulfur Hexafluoroarsenate(V), S8(ASF6),
B. Octaselenium p-Fluorobis@entafluoroantimonate
and Octaselenium Hexafluoroarsenate(V), Se,(AsF,), . . . . . . . . . . . . . . . . . . . . . 21 8
C. Tetraselenium p-Fluorobis(pentafluoroantimonate(V )), Se,(Sb,F,
and Tetraselenium Hexafluoroarsenate(V), Se,(AsF,), . . . . . . . . . . . . . . . . . . . . . 219
D. Tetratellurium p-Fluorobis(pentafluoroantimonate(V)),T e,(Sb,F,
and Tetratellurium Hexafluoroarsenate( V), Te,(AsF,), . . . . , . . . . . . . . . . . . . . . . 220
48. Tetraethylammonium Trichlorogermanate( 1 - ) and Trichlorostannat
A. Tetraethylammonium Trichlorogermanate(1- ) . . . . . . . . . . . . . . . . . .
B. Tetraethylammonium Trichlorostannate( 1 -) . . . . . . . . . . . . . . . . . . . . . . .
49. Weak and Unstable Anionic Bromo and Iodo Complexes . . . . . . . . . .
A. Starting Materials-Chloro Complexes. . . . . . . . . . . . . . . . . . . . . .
1. Triphenylphosphonium Hexachlorocerate(2 -) . . . . . . . . . . . . . . . . . . . . . . . . . 227
2. Triphenylphosphonium Hexachlorolanthanate(3 - ) Salts . . . . . . . . . . . . . . . . 228
3. Tetraethylammonium Tetrachloroferrate(1 -) and Tetrachloroaurate( 1 -) . . 23 1
B. Triphenylphosphonium Hexabromocerate(2 - ) . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 1
C. Hexaiodolanthanide(3 - ) Salts . . . . . . _.. . .. . .. .. . . . . . .. . . . . . ... . . . . . . 232
D. Tetraethylammonium Tetraiodoferr 1 - ) and Tetraiodoaurate( 1 - ) . . . . . . 233
E. Other Iodo Complexes . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
50. Hexahalouranate Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
A. Hexahalouranate(2-) Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
B. General Considerations in Handling [UX,]- Salts. . . . . . . . . . . . . . . . . . . . . . . . . 237
C. Hexachlorouranate( 1 - ) Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
D. Hexabromouranate(1 - ) Salts 239
E. Hexafluorouranate(1 - ) Salts 240
5 1. Pentachloro(trichloroacryly1c hloride)uranium(V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
Index of Contributors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Subject Index . . . . , . . . . . , . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
Formula Index.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
PREFACE
Almost inevitably the content of a volume of INORGANIC SYN-
THESES reflects the interests of the Editor-in-Chief to a considerable
extent. Thus Volume XI11 had a strong flavor of metal-metal bonded
compounds and Volume XIV contains a remarkably fine collection
of solid-state syntheses. The present volume is no exception. It
contains syntheses of many transition-metal compounds important
in homogeneous catalysis, especially complexes of olefins, hydrogen,
and nitrogen, which have interested me and my colleagues. However,
I hope and believe that this volume also has general interest and
that the techniques described will have broad application in inorganic
chemistry. One of the strengths of INORGANIC SYNTHESES
is the diversity of interests among the members of the Editorial
Board. Their help in assembling preparations of all sorts of inorganic
compounds prevents a volume from ever becoming a collection for
just the practitioners of one narrow specialty.
Perhaps the greatest strength of INORGANIC SYNTHESES
is the support that it has received from inorganic chemists generally.
Assembling this volume has done much to restore my faith in human
nature. People have been immensely helpful in soliciting, contribut-
ing, checking, and editing syntheses. At the risk of slighting individ-
uals by omission, I am especially indebted to Charles Van Dyke
for his initiative in assembling the chapter on germanium hydride
derivatives and to George Ryschkewitsch and Roland Koster for
contributing the two groups of syntheses that make up most of the
chapter on boron compounds. Similarly S. D. Robinson contributed
xi