Inorganic Syntheses, Volume 16

301 Pages·36.013 MB·English

INORGANIC
SYNTHESES
Volume XVI
Board of Directors
THERALD MOELLER Arizona State University
WILLIAM L. JOLLY University of California
HENRY F. HOLTZCLAW University of Nebraska
JAY H. WORRELL University of South Florida
F. A. COTTON Texas A & M Unii'ersity
JOHN K. RUFF University of Georgia
AARON WOLD Brown University
GEORGE W.P ARSHALL E.I. du Ponf de Nemours
& Company
Future Volumes
XVII Alan G. MacDiarmid
XVIII Bodie Douglas
XIX Duard F. Shriver
International Associates
E. 0. FISCHER Technische Hochschule (Munich)
JACK LEWIS Cambridge Universify (London)
LAMBERTO MALATESTA University of Milan
GEOFFREY WILKINSON Imperial College of Science
and Technology (London)
Editor-inchief
FRED BASOLO
Department of Chemistry
Northwestern University
Evanston. Illinois
INORGANIC
SYNTHESES
Volume XVI
McGRAW-HILL BOOK COMPANY
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INORGANIC SYNTHESES, VOLUME XVI
Copyright @ 1976 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,
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ISBN 0-07-004015-X
1234567890 KPKP 785432109876
CONTENTS
Preface .......................................................................
ix
Notice to Contributors .........................................................
x
Chapter One METAL NITROSYL COMPLEXES
1
Carbonyltrinitrosylmanganese . .
Tetranitrosylchromium and
..................................................
A. Tetranitrosylchromium .2
B. Carbonyltrinitrosylmanganese ...................................................... ...... 4
Dithiocarbamate Complexes of Iron and Cobalt Nitrosyls ......
A. ...............................
Bis(diethy1dithiocarbamato)nitrosyliron
BB.. BBiiss((ddiimmeetthhyy1lddiitthhiiooccaarrbbaammaattoo))nniittrroossyyllccoobbaalltt ............................
Ammine Complexes of Osmium, Including Amminenitrosyls
A. Iodide .............
Pentaammine(dinitrogen)osmium(II)
BB.. PPeennttaaaammmmiinneeiiooddoooossmmiiuumm((IIII11)) IIooddiiddee .............................................. ......1 0
C. Hexaammineosmium(II1) Iodide ...
D. Pentaamminenitrosylosmium(3+ ) Halide Monohydrate .................
E. Halide .......................
Tetraamminehydroxonitrosylosmium(2+)
F. Tetraamminehalonitrosylosmium(2+) Halide ...........
4. Nitrosylammineruthenium Complexes ...................................
AA.. Tetraamminechloronitrosylrutheni Chloride ...............
Tetraamminechloronitrosylruthenium(2+)
BB.. TTeettrraaaammmmiinneeaacciiddoonniittrroossyylrlurtuhtehneiun ium(2+)P erchlorate
5. Dinitrosylcobalt Complexes . . ......................................... ..... .16
A. (N,N,N',N'-Tetramethylethy rosylcobalt( I+) Tetraphenyl-
.
borate ........................... ...... ......
B. Tetraphenylborate ..........
Bis(triphenylphosphine)dinitrosylcobalt(l+)
C. [ Ethylenebis(diphenylphosphine)]d initrosylcobalt( 1+ ) Tetraphenylborate .
6. I+) .......
Bis(triphenylphosphine)chlorodinitrosylruthenium( Tetrafluoroborate .21
7. Bis(diha10-7-cyclopenta-
Dicarbony1-r)-cyclopentadienylnitrosylmolybdenum and
dienylnitrosylmolybdenum) .......... .............
Derivatives. .24
A.
Dicarbonyl-7-cyclopentadienylnitrosylmolybden
B. ......................
Bis(dichloro-~-cyclopentadienylnitrosylmo~ybdenum) .26
C. ........
Bis(dibromo-r)-cyclopentadienylnitrosylmolybdenum)
........................
D. Bi\(diiodo-q-cyclopentadienylnitrosylmolybdenum) .28
8.
Bis(methyldiphenylphosphine)dichloronitrosylcobalt
A. .....................................
Room-Temperature Form
B. ................... ,. .................
Low-Temperature Form
9. Tris(tripheny1phosphine)nitrosylcobalt
and Tris(tripheny1phosphine)nitrosyl-
................................................
rhodium
. .
A. Tris(tripheny1phosphine)nitrosylcobalt
............. .33
B. Tris(triphenylphosphine)nitrosylrhodium
10. Carbonylchloronitrosylrhenium .....................
Compounds
...................................... .3S
A. Octacarbonyl-di-p- chlorodirhenium
......
B. Pentacarbonyl-tri-p-chloro-nitrosyldirhenium
C. Tetracarbonyl-di-p-chlorodichlorodinitrosyldirheniu
11. Decacarbonyldi-p-nitrosyl-trimetalC ompounds ...................3 9
V
A. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
Decacarbonyldi-y-nitrosyl-triruthenium
B. Decacarbonyl-di-p-nitrosyl-triosmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .40
12. trans-Bis(triphenylphosphine)chloronitrosyliridium( I+) Tetrafluoroborate . . . . . . . .41
Chapter Two METAL CARBONYL COMPOUNDS 45
13. Dodecacarbonyltriruthenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4S
14. Dodecacarbonyltriruthenium . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .47
15. Hexadecacarbonylhexarhodium ............................................. 49
16. Di-y-chloro-bis[ tricarbonylchlororuthenium(II)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
.S
17. Dicarbonyl(q -cyclopentadieny . . . . . . . . . . . . . . . . . . . . .53
l)(thiocarbonyl)manganese(I)
18. Transition Metal Carbonyl Derivatives of Magnesium . . . . . . . . . . . . . . . . . . . . . . . . .S6
A. Bis(dicarbonyl~-cyclopentadienyliron)bis(tetrahydrofuran)magnesium . . . . . . .56
B. . . .
Tetrakis(pyridine)bis(tetracarbonyIcobalt)magnesium
CC..
BB(itises[t[rddaiihccyaadrrbrbooonfnuyylrla--nrq))-m-ccyaycgclnlooeppseeinuntmtaad d.i.i.e .e.n n..y y..l l..( (..t t..r r..ii ..bb ..uu. .tt. y.y. l.l. p.p. h.h. o.o. s..s p..ph ..hi .i.n .n.e .e.) .).m. m.o. o.l. l. .y ..b ..d ..e ..n ..u ..m ..] ..t ..e ..t. .r. a. k. i. s. -. . . .59
(tetrahy drofuran)magnesium
19. ................................
TTrriiss((ppeennttaaccaarrbboonnyyllmmaannggaanneessee))tthhaalllliiuumr(nI(IllII))
20. ((AAl1kk yy11aammiinnoo))ddiifflluuoorroopphho sphine- and Halodifluorophosphinetetracarbonyliron
Complexes ... .. .. .. .. .. .. .. .. .. .. .. .......................................................................... ... 63
Complexes
AA.. (Diethy1amino)difluor .....................
(Diethy1amino)difluorophosphinetetracarbonyliron
B. Chlorodifluorophos .............................
B. Chlorodifluorophosphinetetracarbonyliron
C. Trifluorophosphinetetracarbonyliron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .67
21. Tris[ and Tetraphenylarsonium Hexacarbonyl-
bis(2-methoxyethyl)ether]potassium
metallates(1-) of Niobium and Tantalum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68
A. Hexacarbonylniobate(1-) . . . . . . . . . .69
Tris[bis(2-methoxyethyl)ether]potassium
B. Tris[ bis(2-methoxyethyl)ether] potassium Hexacarbonyltantalate( I - )
C. Tetraphenylarsonium Hexacarbonyltantalate( 1- ) . . . . . . . . . . . . . . . . .
D. Tetraphenylarsonium Hexacarbonylniobate( 1 -) . . . . . . . . . . . . .
Chapter Three WERNER TYPE METAL COMPLEXES 75
22. (Dinitrogen oxide)pentaammineruthenium(II) Salts . . . . . . . . . . .75
23. . . . . . . . . . . . . . . . . . . . . . . . . .78
Tetrakis(isothiocyanato)bis(2,2’-bipyridine)niobium(1V)
24. Malonato Complexes of Chromium(II1) . . . . . . . ........................ 80
A. Potassium Tris(malonato)chromate(III)T rihydrate . . . . . . , . . . . . . . . . . . 80
R. Potassium cis- and Trihydrate . . . . . . . .81
truns-diaquabis(malonato)chromate(III)
2s. Selenoureametal Complexes . . . . . . . . .
A. Perch
Tetrakis(selenourea)cobalt(II)
B. . . .
Sulfatotris(selenourea)cobalt(II)
C. . . . . . . . . . . . . . .86
Dichlorobis(selenourea)mercury(lI)
D.
Dibromobis(selenourea)mercury(II)
E. . . . . . . . . . . . . . . . . . . . . . . . . .86
Di-y-chloro-dichlorobis(selenourea)dimercury(II) ,
26. Nickel Tetrafluorooxovanadate(1V) Heptahydrate . . . 87
27. Polymeric . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .89
Chromium(II1)-bis(phosphinates)
A. Poly[
aquahydroxo-bisb-R.R’-phosphinat0)-chromium(1
B. Poly[ hydroxo-bis(p-R
,R’-phosphinat0)-chromium(IIl)]
28. Resolution of the
cis-Bromoamminebis(ethy1enediamine)co
A. (+)-ci-bromocamphor-~-
(+)-c~is-Bromoamminebis(ethylenediamine)cobalt(lIl)
sulfonate [( +)(+ )-diastereoisomer] . . . . . . . . . . .
B. ( - )-cis-Bromoamminebis(ethy1enediamine)coba
C. (+ )-cis-Bromoamminebis(ethylenediamine)cobalt(III)C hloride . . . . . . . . . . . . . .9S
D. 111) Chloride . . . . . . . . . . . . . .96
(-)-cis-Bromoamminebis(ethylenediamine)cobalt(
29. Complexes . . . . . . . . . . . . . . . . . . . . . . . . . .97
Bis(alkylphosphine)trichlorotitanium(III)
A. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .98
Bis(methylphosphine)trichlorotitanium(III)
B. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .lo0
Bis(dimethylphosphine)trichlorotitanium(III)
C.
Bis(trimethylphosphine)trichlorotitanium(III)
D.
Bis(triethylphosphine)trichlorotitanium(III)
Chapter Four OTHER TRANSITION METAL COMPLEXES 103
Reagents for the Synthesis of 7-Diene Complexes of Tricarbonyliron and Tricar-
30.
bonylruthenium .......................
A.
(Benzylideneacetone)tricarbonyliron(O
B. ( 1, S-C yclooctadiene)tricarbonylruthen’
Complex
31. Bis(T-cyclopentadieny1)niobium
............................
A. Dichlorobis(7-cyclopentadienyl)niobium(IV)
...
B. Bis(7)-cyclopentadienyl)(tetrahydroborato)niobium(III)
C. Bis(.r)-cyclopentadienyl)hydrido(dimethylphenylphosphine)
D. Bis(r)-cyclopentadienyl)dihydrido(dimethylphenylphosphine)n.i.o.b.i.u.m.(.V.). .....
........... 111
Hexafluorophosphate or Tetrafluoroborate
E.
Bromobis(7-cyclope
111) ..........
bum(
32. and rrcrns-Dichlorobis(pyridine)(
Dichloro(1 ,3-propanediyl)platinum 1,3-propane-
................................................
diy1)platinum Derivatives
A. . ................................
B. Dichloro( 1,3-propanediyl)platinum ............. .I
truns-Dichlorobis(pyridine)(2-phenyl-1,3-propanediyl)platinum IS
Olefin@-diketonato)silver(I) Compounds ...................................
33. .117
A. ,S-cyclooctadiene)dver(l) .....
(1,1,1,5,5,S-hexafluoro-2,4-pentanedionat1o )( .I17
B. Olefin@-diketonato)silver(I) ........................................... ,118
Trichloromethyltitanium and Tribromomethyltitanium ....................... ,120
34.
A. Trichloromethyltitanium
B. Tribromomethyltitanium
and Related Complexes ......... .I27
3s. Ethylenebis(triphenylphosphine)palladium(O)
A. Ethylenebis(triphenylphosphine)palladium(O) . .
B. and Ethylenebis(tri-o-tolyl
Ethylenebis(tricylohexylphosphine)palladium(O)
phosph ite)palladium(0 ) ..................................
Chapter Five MAIN-GROUP AND ACTINIDE COMPOUNDS 131
36. Tetraethylammonium, Tetraphenylarsonium, and Ammonium Cyanates and
Cyanides .....................................
A. Tetraethylammonium Cyanate and Cyanide . .
B. Tetraphenylarsonium Cyanate and Cyanide .............................
,134
C. Ammonium Cyanate . . ,136
Diindenylmagnesium ......................................................
37. 137
Fluoromethylsilanes .....................................................
38. .I39
A. Trifluoromethylsilane ....
,139
B. Difluorodimethylsilane .......... ....
,141
Uranium Hexachloride ...................................................
39. .143
Complexes Uranium(1V) and Thorium(1V).. ...
40. Chlorotris(7-cyclopentadienyl) of I47
A. Chlorotris(r)-cyclopentadienyl)uranium(IV) .............................. ,148
B. ..............................
Chlorotris(7-cyclopentadienyl)thorium(IV) .I49
Chapter Six LIGANDS USED TO PREPARE METAL COM-
PLEXES 153
Trimethylphosphine ......................................................
41. IS3
Tertiary Phosphines . .
42.
A. Methyldiphenylpho
B. Ethyldiphenylphosphine .... ..................................
158
C. n-Butyldiphenylphosphine .....................................
D. Cyclohexyldipheny .........................
IS9
E. Benzyldiphenylphosphine
.................................... .160
F. 2-(Diphenylphosphino)triethylamine
Diphenylphosphine ....................................................... 161
43.
................. ....
44. Tribhenyl-4)phosphine ,164
45. Methyl Difluo~r~ ophosphite .................................................... . .1 66
46. Bi-, Tri-, and Tetradentate Phosphorus-Sulfur Ligands ......................
A. ...............................
[o-(Methylthio)phenyl]diphenylphosphine
B. ..............................
Bis[o-(rnethylthio)phenyl]phenylphosphine
C. ...................................
Tris[o-(rnethylthio)phenyl]phosphine
47. Tetradentate Tripod Ligands’ Containing Nitrogen, Sulfur, Phosphorus, and Ar-
sseenniicc aass DDoonnoorr AAttoommss ..................... .........................................
A. ...................
Tris[ 2-(dipheny1phosphino)e thyl] arnine
B. Tris[2-(diphenylarsino)ethyllarnine .......................
C. 2-(rnethylthio)ethyl]amine ... ...........
Tris[ ,177
48. Dimethyl(pentafluoropheny1)phosphine and Dimethyl(pentafluoropheny1)arsine
................................... ............... 180
....... ..............
fluoropheny1)phosphine .I81
B. .....................................
Dirnethyl(pentafluoropheny1)arsine ,183
....
49. Tris(o-dimethy1arsinophenyl)arsinea nd Tris(o-dimethylarsinopheny1)stibine ,184
.....
A. Tris(o-dimethylarsinopheny1)arsine 186
B. .....
Tris(o-dirnethylarsinophenyl)stibine 187
50. cis-2-Diphenylarsinovinyldiphenylphosphine 2-Diphenylarsinoethyldi-
and
............ .............
phenylphosphine
A. cis-2-Diphenylarsinovinyldi
B. ........... ..............
2-Diphenylarsinoethyldiphenylphosphine ,191
51. [ 2-(Isopropylphenylphosphino)ethyl]di
52. [ (Phenylisopropylphosphino)rnethyl]diphenylphosphineS ulfide ...............,1 95
................
53. N.N.N~N‘-Tetrakis(diphenylphosphinomethyl)ethylenediarnine I98
. .
54. Ethylenebis(nitrilodirnethylene)letrakis(phenylphosphinica cid)
55. ........
[2-(Phenylphosphino)ethyl]diphenylphosphine
A. Isopropylphenylvinylphosphinate ....... .............
.203
B. [ 2-(Phenylphosphino)ethyl]diphenylphosphine ........................... ,204
56. I,1 , I-Trifluoro-4-mercapto-4-( 2-thienyl)-3-but en-2-one ........................ ,206
Chapter Seven COMPOUNDS OF BIOLOGICAL INTEREST 213
.......................................................
57. Metalloporphyrins .21 3
A. meso-Tetraphenylporphyrincopper1(1 ) .................................. .21 4
B. .............
Hematoporphyrin IX dimethylesterchloroiron(II1) 216
58. -(.1 ,4..,~8..,.U1lL-"Tpe"t, rava.z,JaLc LyL l.c' l1oteurtllrlrarrd.,elrcvrarln~.eI.)U.n"Li."cLkL,eI.lI, (lI)P erchlor . . . . . , . , . . . . . . . . . . . . . . . .
58. (c1y,c4l,o8t,Ie It-rTaedtercaaanzea c.y.c.l.o.t.e tradecane)nickel(Il)P erchlorate and I ,4,8,1l-Tetraaza-
.........................................................
cAy.cl (o1t,e4t1r8a,dlIe -caTneet raazacy
AB.. (1 1.,44.;88.,11 II--TTeettrraaaazzaaccyyccllootteettrraadde cane)nickel(ll)P erchlorate . . . . . . . . . . . . . . . . .
59. NB,.N ’1-.E4t.8h, yIl Ie-nTeebtirsa(arznaocnyoctlhoitoeatcreatdyelcaacneet o.n .i .r .n .i .n .a .t .o ). c. o. b. a. l. t. (, l. la.) n. d. .R .e .l .a .t .e .d . .M .e .t .a .l . . . .
..................................................
Complexes
A. ........................... ,226
N.N’-Ethylenehis(monothioacety1acetoniniine)
B. ................
N,N’-Ethylenebis(monothioacetylacetoniminato)cohalt(II) .227
60. ..........................................................
Metallatranes ..229
A. ................
I-Ethyl-2,8,9-trioxa-S-aza-germatricyc3l.o3[. 3.0lundecane .229
B. ................
l-Ethyl-2,8,9-trioxa-5-aza-stannatricyc3lo.[3 .3.0lundecane 230
...............
C. 2,8-Dioxa-5-aza-l-stannobicycl2o.[2 .0loctane
61, ..........
cis-Bis(diethyldithiocarbamato)dinitrosylmolybdenum
of ..... ...............
62. Some 7-CyclopentadienylC omplexes Titanium(II1) ,237
A. Dichloro(7-cyclopentadienyl)titanium(IIl)P olymer .......... ..... ,238
B. ....
Dichloro(~-cyclopentadienyl)bis(dimethylphenylphosphine)titan ,239
Indexc?fContributors .........................................................
243
Subject Index ................................................................
,247
Formula Index ...............................................................
,253
PREFACE
This volume contains checked synthetic procedures for 130 compounds.
An attempt is made to group syntheses in different chapters in accordance
with specific areas of interest. For example, the first chapter presents the
syntheses of some metal nitrosyls and the last chapter is devoted to the
preparation of a few compounds of biological interest. There is also a
chapter on the syntheses of ligands, which might be more appropriate for
a volume of Organic Syntheses. My justification for including this chapter
is that the compounds are often prepared by inorganic chemists and the
ligands are certainly largely used by coordination and/or organometallic
chemists. Other syntheses are grouped in different chapters with more
traditional headings.
Inorganic Syntheses, Inc., is a nonprofit organization dedicated to the
selection and presentation of tested procedures for the synthesis of
compounds of more than routine interest. The Editorial Board seeks the
cooperation and help of the entire scientific community in its attempt to
realize these goals. Persons familiar with the syntheses of important
compounds should take the initiative to prepare manuscripts suitable for
INORGANIC SYNTHESES and to encourage others in the field to do
likewise. Equally important are the persons willing to devote the time to
check these procedures and to work out with the submitter any significant
alterations that may improve the synthesis. My experience in working
with submitters and checkers has been most gratifying, and I am pleased
to acknowledge their cooperation and help in preparing Volume XVI.
Directions for submitting syntheses for INORGANIC SYNTHESES
follow this Preface. The editor for Volume XVII is A. G. MacDiarmid, for
Volume XVIII is B. E. Douglas, and for Volume XIX is D. F. Shriver.
Finally I thank those members of Inorganic Syntheses, Inc.. who read
the original manuscripts and gave me valuable advice and help. I am espe-
cially thankful to Professors Robert D. Feltham and Devon W. Meek for
contacting prospective authors for syntheses of metal nitrosyls and of
ligands, respectively. I also thank S. Kirschner and W. H. Powell for their
help.
Fred Basolo
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 all chemists will share in the responsibility of producing INORGANIC
SYNTHESES by offering their advice and assistance in both the formu-
lation 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 re-
search. However, syntheses of individual compounds that are of interest
or importance are also acceptable.
The Editorial Board lists the following criteria of content for submitted
manuscripts. Style should conform with that of previous volumes of IN-
ORGANIC 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 pro-
cedure. The Procedure should present detailed and unambiguous labora-
tory 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 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
xi