Inorganic Syntheses, Volume 13

305 Pages·1972·45.28 MB·English

INORGANIC
SYNTHESES
Volume XIIl
.................... ..................................
Editorial Board
FRED BASOLO Northwestern University
HOWARD C. CLARK University of Western Ontario
W. A. G. GRAHAM University of Alberta
M. FREDERICK HAWTHORNE University of California (Riverside)
RICHARD H. HOLM Massachusetts Institute of Technologv
ALAN G. MacDIARMID University of Pennsylvania
GEORGE W. PARSHALL E. I. du Pont de Neumours and Company
JOHN K. RUFF University of Georgia
AARON WOLD Brown Univehity
Secretary, Editorial Board
STANLEY KIRSCHNER Wayne State University
International Associates
E. 0. FISCHER Technische Hochschule (Munich)
JACK LEWIS University College (London)
LAMBERTO MALATESTA University of Mi[a?i
GEOFFREY WILKINSON Imperial College of Science
and Technology (London)
Editor-in- Chief
F. A. COTTON
Projessor, Department of Chemistry
.................M..a.s.s.a.c.h.u.s.e.t.t.s. I.n.s.t.i.t ute of Technology
Cambridge, Massachusetts
INORGANIC
SYNTHESES
Volume XI11
McGRAW-HILL BOOK COMPANY
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INORGANIC SYNTHESES, VOLUME XI11
Copyright @ 1972 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
07-013208-9
1234567890 MAMM 765432
To JANET D. SCOTT
in appreciation of her many contributions
to INORGANSYICN THESiEnS t he areas of
nomenclature and indexing.
CONTENTS
Preface . . . . . . . . . . . . . . . . . . . . xi
Notice to Contributors . . . . . . . . . . . . . . . . xv
Chapter One COMPOUNDS OF THE NONTRANSITION
ELEMENTS . . . . . . . . . . . . 1
1 . Perbromic Acid and Potassium Prebromate . . . . . . . . 1
2 . a-Sulfanuric Chloride-Cyclic Trimer . . . . . . . . . . 9
A . Chloride . . . . . . 10
(Trichlorophosphorany1idene)sulfamoyl
B . a-Sulfanuric Chloride-Cyclic Trimer . . . . . . . . . 11
3 . Arsine and Arsine-d3 . . . . . . . . . . . . . . . 14
4 . Ammonium Cyanate . . . . . . . . . . . . . . . 17
5. Phosphorus(II1) Isocyanate . . . . . . . . . . . . . 20
6 . Phosphoramidic Acid and Its Salts . . . . . . . . . . . 23
A . Ammonium Hydrogen Phosphoramidate . . . . . . . . 23
B . Phosphoramidic Acid . . . . . . . . . . . . . . 24
C . Potassium Hydrogen Phosphoramidate . . . . . . . . . 25
7 . and
Diphenyl(trimethy1silyl)phosphine
. . . . . . . . . . . 26
DimethyI(trimethylsily1)phosphine
A . . . . . . . . . . . 27
Diphenyl(trimethy1silyl)phosphine
B . . . . . . . . . . . 29
Dimethyl(trimethylsi1yl)phosphine
8. Exchange Reactions for the Syntheses of Phenylboron Chlorides and
Tetrafluoromethylphosphorane . . . . . . . . . . . . 32
A . Dichloro(phenyl)borane, C6H5BC12 . . . . . . . . . . 35
B . Chlorodiphenylborane, (C6H,) ?BC1 . . . . . . . . . . 36
C . Tetrafluoromethylphosphorane, CH3PF4 . . . . . . . . 37
9 . 2,4, 6-Trichloroborazine . . . . . . . . . . . . . . 41
10. 2,4,6-Trichloro-lJ3, 5-trimethylboraeine . . . . . . . . . . 43
Chaptqr Two ORGANOMETALLIC COMPOUNDS . . . . 47
11. Cyclic-diolefin Complexes of Platinum and Palladium . . . . . . 47
A . Platinum Compounds . . . . . . . . . . . . . . 48
vii
viii Contents
B . Palladium Compounds . . . . . . . . . . . . . 52
12. Cationic Diene Complexes of Palladiuni(I1) and Platinum(I1) . . . 55
A . Complexes of Type (I). . . . . . . . . . . . . . 56
B . Complexes of Type (11) . . . . . . . . . . . . . 59
C . Complexes of Type (111) . . . . . . . . . . . . . 61
D . Complexes of Type (IV) . . . . . . . . . . . . . 62
13. Trichloro-, Trimethyl-, and Trifluorosilylcobalt Tetracarbonyl . . . 65
A . . . . . . . . . . . 67
Tetracarbonyl(trichlorosily1)cobalt
B . . . . . . . . . . . 69
Tetracarbonyl(trimethylsily1)cobalt
C . . . . . . . . . . . 70
Tetracarbonyl(trifluorosily1)cobalt
14. Isoleptic Allyl Derivatives of Various Metals . . . . . . . . 73
A . Allyl Magnesium Chloride . . . . . . . . . . . . . 74
B . Tetraallylstannane . . . . . . . . . . . . . . . 75
C . Tetraallylsilane and Tetraallylgermane . . . . . . . . . 76
D . Tri-h3-allylchromium . . . . . . . . . . . . . . 77
E . Di-h3-allylnickel . . . . . . . . . . . . . . . . 79
Chapter Three COMPOUNDS CONTAINING METAL-TO-
METAL BONDS . . . . . . . . 81
15. Rhenium and Molybdenum Compounds Containing Quadruple Bonds . 81
A . Octahalodirhenate(II1) Anions . . . . . . . . . . . 82
3 . Compounds . . . . 85
Tetrakis(carboxylato)dihalodirhenium(III)
C . (11) Compounds . . . . . 87
Tetrakis(carboxy1ato)dimolyndenum
16. Tetrakis(acetato)dirhodium(II) and Similar Carboxylato Compounds . 90
17. Dodecacarbonyltriruthenium and -triosmium . . . . . . . . 92
A . Dodecacarbonyltriruthenium . . . . . . . . . . . . 92
B . Dodecacarbonyltriosmiuin . . . . . . . . . . . . . 93
18. Dodecacarbonyltetrairidium . . . . . . . . . . . . . 95
19. Disodium . . . . . 99
Hexaalkoxy-octa-p3-chloro-hexamolybdates
A . Disodium . . . 1 00
Octa-p3-chloro-hexaniethoxyhexamolybdate(I1)
B . Disodium . . . . 1 01
Octa-p3-chloro-hexaethoxyhexamolybdate(I1)
C . Disodium Octa-p3-chloro-hexamolybdate(II) . . . . . . . 1 02
Chapter Four PHOSPHINE AND PHOSPHITE COMPLEXES
OF LOW-VALENT METALS . . . . . .
105
20 . Triaryl Phosphite Complexes of Cobalt, Nickel. Platinum. and Rhodium . 105
A . Hydridotetrakis(tripheny1p hosphite)cobalt(I) . . . . . . . 1 07
B . Tetrakis(tripheny1 phosphite)nickel(O) . . . . . . . . . 1 08
C . Tetrakis(tripheny1 phosphite)platinum(O) . . . . . . . . 109
D . Hydridotetrakis(tripheny1 phosphite)rhodium(I) . . . . . . 1 09
21 . Tetrakis (triethyl phosphite)nickel(O), Palladium (0). and Platinum (0)
Complexes . . . . . . . . . . . . . . . . . . 112
A . Tetrakis(triethy1 phosphite)nickel(O) . . . . . . . . . 112
B . Tetrakis(triethy1 phosphite)palladium(O) . . . . . . . .
113
C. Tetrakis(triethy1 phosphite)platinum(O) . . . . . . . . 1 15
D . Tetrakis(tripheny1 phosphite)nickel(O) . . . . . . . . . 116
22 . Low-valent Metal Complexes of Diethyl Phenylphosphonite . . . 1 17
A . Tetrakis(diethy1 . . . . . . . 1 18
phenylphosphonite)nickel(O)
B . Tetrakis(diethy1 (I) . . . . . 1 18
pheny1phosphonite)hydridocobalt
C . Tetrakis(diethy1 . . . . . 1 19
phenylphosphonite)dihydroiron(II)
23. . . . . . . . . . 121
Tetrakis(triphenylphosphine)palladium(O)
24 . . . . . . . . . . . 124
Tetrakis(triphenylphosphine)nickel(O)
25 . . . . . . . 1 26
Carbonylhydridotris(triphenylphosphine)iridium(I)
26 . . . . . . . 131
Chlorohydridotris(triphenylphosphine)ruthenium(II)
Chapter Five BINARY COMPOUNDS OF THE TRANSITION
METALS . . . . . . . . . . . . . 1 35
27. Single Crystals of Transition-metal Dioxides . . . . . . . . 135
A . Ruthenium and Iridium Dioxides . . . . . . . . . . 1 37
B . Osmium Dioxide . . . . . . . . . . . . . . . 140
C . Tungsten Dioxide and @-RheniumD ioxide . . . . . . . . 1 42
28 . Molybdenum(V) Fluoride . . . . . . . . . . . . . 146
29 . Tungsten(V) Chloride . . . . . . . . . . . . . . . 150
30 . Anhydrous Nickel(I1) Halides and Their Tetrakis(ethano1) and
1,2 -dimethoxyethane Complexes . . . . . . . . . . . . 1 54
A . Nickel(I1) Chloride Dihydrate . . . . . . . . . . . 156
B . Nickel(I1) Bromide Dihydrate . . . . . . . . . . . 1 56
C . . . . . . . . . . . 158
Dichlorotetrakis(ethanol)nickel(II)
D . . . . . . . . . . . 1 60
Dibromotetrakis(ethanol)nickel(II)
E . Dichloro (1, . . . . . . . . 1 60
2-dimethoxyethane)nickel(II)
F . Dibromo(1, . . . . . . . . 1 62
P.dimethoxyethane)nickel(II)
G . Bis(1, . . . . . . . . 1 63
2-dimethoxyethane)diiodonickel(II)
Chapter Six HALO COMPLEXES OF SOME METALS 165
<.l Tetraphenylarsonium . . . . . . . 1 65
Tetrachlorovanadate(II1)
12 . Tris(tetraethy1ammonium) . . . . . 1 68
Nonachlorodivanadate(II1)
13. Ammonium, Rubidium. and Cesium Salts of the Aquapentachloro-
molybdate(II1) and Hexachloromolybdate(II1) Anions . . . . . 1 70
A . Salts . . . . . . . . . 1 71
Aquapentachloromolybdate(II1)
B . Ammonium Hexachloromolybdate(II1) . . . . . . . . . 172
14 . Disodium Hexachloroplatinate(1V) . . . . . . . . . . . 173
Chapter Seuerz VARIOUS TRANSITION-METAL
COMPOUNDS . . . . . . . . . . . 1 77
.5. Chloride . . . . . . 1 77
Dichlorotetrakis(2-propanol)vanadium(III)
i6 . . . . . . . . . 1 79
Trichlorobis(trimethylamine)vanadium(III)
;7. Vanadyl(1V) Acetate, VO(CH,CO,), . . . . . . . . . . . 1 81
23 . Tris(diamine)c hromium (111) Salts . . . . . . . . . . . 1 84
.9. 2.dithiolato(l or 2 -)] Complexes of Cobalt
Bis[cis.l,2.dicyanoethene.l,
and Iron . . . . . . . . . . . . . . . . . . 1 87
Contents
x
A . Sodium Cyanodithioformate.iV, N.dimethylformamide(1/3) . . . 1 87
B . The Formation of the Ligand Solution . . . . . . . . . 1 88
C . Bis(tetrapheny1phosphonium) e.
Bis[cis.1,2.dicyanoethen
1,Z dithiolato(2 -)]cobaltate(2-) . . . . . . . . . . 1 89
D . Bis(tetrapheny1phosphonium) Tetrakis(cis.1,2.dicyanoethen e.
1,2 .dithiolato)dicobaltate(2 -) . . . . . . . . . . . 1 91
E . Bis(tetraethy1ammonium e.
Tetrakis(cis.1,2.dicyanoethen
1,2 .dithiolato)diferrate(2 - . . . . . . . . . . . . 1 92
j
40 . Resolution of the Ion . . 195
(Ethylenediamine)bis(oxalato)cobaltate(III)
41 . Nitrito Complexes of Nickel(I1) and Cobalt(I1) . . . . . . . 2 02
42 . Ruthenium Ammines . . . . . . . . . . . . . . . 2 08
A . Hexaammineruthenium(I1) Dichloride . . . . . . . . . 2 09
B . Hexaamrnineruthenium(I1) Tetrachlorozincate . . . . . . 2 10
C . Pentaamminechlororuthenium(II1) Dichloride . . . . . . . . 210
D . Hexaamminerutheniuni (111) Tribromide . . . . . . . . 2 11
43. Pentaamminechlororhodium (111) Dichloride and
Pentaaminehydridorhodium(II1) Sulfate . . . . . . . . . 2 13
A . l'entaarnminechlororhodium(II1) Chloride . . . . . . . . 2 13
B . Pentaamminehydridorhodium(II1) Sulfate . . . . . . . . 2 14
. Dichloro (ethylenediamine)palladium(II) and
44
(2,2' -Bipyridine)dichloropalladium(I1) . . . . . . . . . . 2 16
A . Dichloro (ethylenediamine)palladium(II) . . . . . . . . 2 16
. (2,2' -Bipyridine)dichloropalladium(II) . . . . . . . . . 2 17
B
45 . Nonahydridorhenate Salts . . . . . . . . . . . . . . 2 19
A . Disodium Nonahydridorhenate . . . . . . . . . . . 2 19
B . Bis(tetraethy1ammonium) Nonahydridorhenate . . . . . . 2 23
46 . Potassium . . . . . . . . 2 26
Hexakis(isothiocyanato)niobate(V)
CORRECTIO.NS. . . . . . . . . . . . . . . . . . 2 32
Diaquahydrogen trans-Dichlorobis (ethy1enediamine)cobalt (111)
Dichloride . . . . . . . . . . . . . . . . . . 2 32
Sulfate: A Modified Procedure 233
Tris(ethylenediaminejchromium(III)
Index of Contributors . . . . . . . . . . . . . . . . 2 35
Subject Index . . . . . . . . . . . . . . . . . . . 2 39
Formula Index . . . . . . . . . . . . . . . . . . 2 57
PREFACE
In Volume XIII, detailed and checked synthetic procedures are
presented for 120 compounds. These compounds are of three
main classifications. First there are a number of compounds
of the transition elements. Many of these are classical or
Werner complexes and a few are organometallic compounds.
There are also a few procedures dealing with the nonclassical
compounds involving metal atom clusters or very strong multi-
ple metal-metal bonds. A few more words about one of the
latter will be found below. The second large group of com-
pounds are those of nontransition elements. In the present vol-
ume this group is a rather diverse array, not strongly organized
around any principal theme.
Although they are transition-metal compounds, I have chosen
to place a group of complexes involving low-valent metals
coordinated by various phosphorus ligands in a separate cate-
gory, since they have an exceptional degree of both practical
and fundamental interests. It is only relatively recently that the
ability of many other ligands besides carbon monoxide, and
most particularly various XsP-type ligands, to stabilize metals
in zero or other low formal oxidation states has been generally
appreciated. It is now clear, however, that aryl phosphines
and phosphites in general have this ability, and a number of
compounds have been prepared. Many of these have shown
promise as catalysts and are of interest, therefore, industrially
as well a.s academically.
xi