Editor-in-Chief

ALVIN P. GINSBERG

INORGANIC SYNTHESES

Volume 27

A Wiley-Interscience Publication JOHN WILEY & SONS

New York Chichester Brisbane Toronto Singapore

INORGANIC SYNTHESES

Volume 27

.................... ................ Board of Directors

JOHN P. FACKLER, JR. BODlE E. DOUGLAS SMITH L. HOLT, JR. JAY H. WORRELL RUSSELL N. GRIMES ROBERT J. ANGELIC1

Texas A&M University University of Pittsburgh

Oklahoma State Uniuersity University of South Florida

University of Virginia Iowa State University

Future Volumes

28 ROBERT J. ANGELIC1 Iowa State University 29 RUSSELL N. GRIMES University of Virginia 30 LEONARD V. INTERRANTE Rensselaer Polytechnic Institute 31 ALLEN H. COWLEY University of Texas, Austin 32 MARCETTA Y. DARENSBOURG Texas A&M University

International Associates

MARTIN A. BENNETT FAUSTO CALDERAZZO 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 AKlO YAMAMOTO

Australian National University, Canberra

University of Bristol Imperial College of Science and Technology. London

Tokyo Institute 01 Technology. Yokohama

Editor-in-Chief

ALVIN P. GINSBERG

INORGANIC SYNTHESES

Volume 27

A Wiley-Interscience Publication JOHN WILEY & SONS

New York Chichester Brisbane Toronto Singapore

A NOTE TO THE READER This book has been electronically reproduced from digital idormation stored at John Wiley h Sons, Inc. We are phased that the use of this new technology will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them. The content of this book is identical to previous printings.

Published by John Wiley & Sons, Inc.

Copyright $? 1990 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 0-471-50976-0

To John C. Bailar, Jr., Associate Editor of Volumes 1-111 and

Editor-in-Chief of Volume IV, in appreciation of his contributions to

the development of Inorganic Syntheses.

PREFACE

Inorganic Syntheses is 50 years old. The first volume, edited by Harold S. Booth, appeared in 1939 and contained 90 checked procedures. Booth, Professor of Chemistry at Western Reserve University, had seen a need for a series of volumes in which would appear detailed and tested procedures for the synthesis of inorganic compounds. His efforts to bring Inorganic Syntheses into being dated back to 1933 when he was joined in the venture by L. F. Audrieth, W. C. Fernelius, W. C. Johnson, and R. E. Kirk. To quote one of the cofounders: “It would be fair to say that the inauguration of Inorganic Syntheses was not a product of the times but more a reaction against the times. In the late 20’s and early 30’s of this century there were in this country only a few inorganic chemists and little research in the field” [W. C. Fernelius, “History of Inorganic Syntheses,” October 1983 (unpublished)].

Over the 50 years since Volume 1 appeared, research in inorganic chemistry has undergone an enormous expansion, and the Inorganic Syntheses series has grown to a total of 27 volumes containing more than 3000 checked procedures. Although it would be incorrect to claim that all of these procedures are foolproof [witness Inorg. Synth., 23, 199 (1985)], they do comprise the largest available collection of reliable preparations of inorganic compounds. The series has established itself as the reference of first resort for anyone with the need to synthesize an inorganic compound. The procedures in Inorganic Syntheses owe their reliability to the requirements that they be checked in a laboratory other than that of the submitters and that they be presented in detailed and unambiguous form. Both of these requirements frequently result in substantial modification of submitted manuscripts.

The present volume contains over 200 syntheses, presented in 68 numbered sections grouped into nine chapters that correspond for the most part to

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 Prrfuce

currently active areas of research. Although all of the chapters contain important and timely compounds, I would single out for special mention Chapter 3 on the early transition metal polyoxoanions. This chapter, organized and solicited by Walter G. Klemperer, addresses the synthesis of a class of compounds that are notably difficult to prepare in pure form. The successful preparation of many of these compounds requires close attention to the details of the procedure, and in several cases critical details taken for granted by the submitters were brought out by the checkers.

An Inorganic Syntheses volume is the product of the efforts of many people. There are, of course, the submitters and checkers who produce the checked syntheses. In addition to these contributors, I would like to thank the following people for their efforts on behalf of Volume 27: Walter Klemperer for organizing Chapter 3 and providing an introduction to it; Andrea Wayda for organizing Chapter 4; Thomas E. Sloan and William Powell for advice on chemical nomenclature and for compiling the index; and the members of the Inorganic Syntheses Corporation who provided reviews of the submitted manuscripts, especially Bob Angelici, John Bailar, Dimitri Coucouvanis, and Therald Moeller. John Bailar and Therald Moeller also helped with checking the revised manuscripts. Finally, I thank Fred Basolo for efficiently resolving an awkward checking problem and Duward Shriver for his “Guide for Editors of Inorganic Syntheses”, which facilitated my task as Editor-in-Chief.

ALVIN P. GINSBERG

Berkeley Heights, New Jersey February. 1990

NOTICE TO CONTRIBUTORS AND CHECKERS

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 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 commercially at reasonable prices are not acceptable. We do not encourage the submission of compounds that are unreasonably hazardous, and in this connection, authors are requested to avoid procedures involving perchlorate salts due to the high risk of explosion in combination with organic or organometallic substances. Authors are also requested to avoid the use of solvents known to be carcinogenic.

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. I t 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 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

ix

x Notice to Coniributors and Checkers

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 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.

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 LABORATORY HAZARDS

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 Enuironment published by the American Conference of Governmental 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 tetramethyl- diphosphine disulfide [Inorg. Synth., 15, 186 (1974)] is cited in Inorganic Syntheses, Volume 23, p. 199.

xi

CONTENTS

Chapter One TRANSITION METAL POLYHYDRIDE COMPLEXES

1. Molecular Hydrogen Complexes of Mo and W . . . . . . . . . . . A. Tricarbonyl(dihydrogen)bis(tricyclohexylphosphine)-

molybdenum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Tricarbonyl(q6-cycloheptatriene)tungsten. . . . . . . . . . . . . C. Tricarbonyl(dihydr0gen)bis-

(tricyclohexy1phosphine)tungsten . . . . . . . . . . . . . . . . . . . D. Tricarbonyl(dihydr0gen)bis-

(triisopropy1phosphine)t ungsten . . . . . . . . . . . . . . . . . . . . 2. Molybdenum and Tungsten Phosphine Polyhydrides . . . . . . .

A. Tetrahydridotetrakis(methyldipheny1phosphine)- molybdenum(1V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

B. Tetrahydridotetrakis(methyldipheny1phosphine)- tungsten(1V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

C. Hexahydridotris(dimethylphenylphosphine)tungsten(VI) . D. Hexahydridotris(tricyclohexylphosphine)molybdenum(VI)

Octahydridotetrakis(triphenylphosphine)dirhenium(IV). . . . . . A. Heptahydridobis(triphenylphosphine)rhenium(VII) . . . . . B. Octahydridotetrakis(triphenylphosphine)dirhenium(IV) . . C. Octahydridotetrakis(triphenylphosphine)dirhenium(IV) . .

4. Tetrahydrid~(~~-pentamethylcyclopentadienyI)iridium . . . . . . . 5. Tris[ 1,3-bis(diphenylphosphino)propane]-

heptahydridotriiridium(2 + ) Bis(tetrafluoroborate) and Bis[ t,3-bis(diphenylphosphino)propane]- pentahydridodiiridium( 1 + ) Tetrafluotoborate. . . . . . . . . . . . . . A. (q-I, 5-cyclooctadiene)[l, 3-Bis(diphenylphosphino)-

propaneJiridium Tetrafluoroborate . . . . . . . . . . . . . . . . . . . .

Heterobimetallic Hydride Complexes . . . . . . . . . . . . . . . . . . . A. mer-Trichlorotris(dimethylphenylphosphine)osmium(III) . B. Bis[l, l(~5)-CyclopentadienylJ-

3. Haptahydridobis(triphenylphosphine)rhenium(VII) and

B. CI~,(~PPP),H~ICBF~I~ and CI~~(~PPP)~H~ILBFJ * * * * *

6.

1

3 4

6

7 8

9

to 11 13

14 15 16 16 19

22

23 24 26 27

xiii

xiv Conrents

tris(dimethylphenylphosphine-2~P)-tri-p-hydrido- 1 -hydridoosmiumzirconium . . . . . . . . . . . . . . . . . . . . . . . 27

tris(dimethylpheny1phosphine- 1 KP)- tri-p-hydridoosmiumrhodium . . . . . . . . . . . . . . . . . . . . . . 29

C. [2(q4)-l, 5-Cyclooctadienel-

7. p-Hydrido-tetrakis(tertiary ph0sphine)diplatinum Cations . . . 30 A. p-Hydrido-dihydridotetrakis(triethy1phosphine)-

B. Di-p-hydrido-hydridotetrakis(triethy1phosphine)-

C. Di-p-hydrido-hydridotetrakis(tripheny1phosphine)-

diplatinum(I1) Tetraphenylborate( 1 -) . . . . . . . . . . . . . . . 32

34

36

diplatinum(I1) Tetraphenylborate(1 - ). ................

diplatinum(I1) Tetraphenylborate( 1 -) . . . . . . . . . . . . . . .

Chapter Two TRANSITION METAL CHALCOGENIDE COMPLEXES

8. Tetraphenylphosphonium Salts of [Mo~(S) , (S,)~- , ]~ - Thioanions and Derivatives. . . . . . . . . . . . . . . . . . . . . . . . . . . 39 A. Bis(tetrapheny1phosphonium) Tetrathiomolybdate(VI),

(Ph,P),[MoS,] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 B. (Ph4 p)2 [(Mo2S10)0.72(Mo2Si 2)0.261'+HC0N(CH 312. * * 42 C. Bis(tetrapheny1phosphonium) Di-pthio-

D. Bis(tetrapheny1phosphonium) (q2-Disu1fido)- tetrathiodimolybdate(V), (Ph,P)2[MO2S6]. . . . . . . . . . . . 43

(Ph, P)2 [MoZS7]* HCON(CH,), . . . . . . . . . . . . . . . . . . .

dit hiodimoly bdate(V), (Ph, P)2 [ Mo S , ] . . . . . . . . . . . . . . 9. Molybdenum-Sulfur Clusters . . . . . . . . . . . . . . . . . . . . . . . . . 47

di-p-thio-trithiodimolybdate(IV, VI), 44

45 E. Bis(tetrapheny1phosphonium) Bis(q'-disulfido)-di-p-thio-

A. Diammonium Tris(p-disulfido)tris(disulfido)-p3-thio- rtianguto-trimolybdate(1V) Hydrate . . . . . . . . . . . . . . . . . 48

B. Diammonium Bis(p-disulfido)tetrakis(disulfido)- dimolybdate(V) Dihydrate . . . . . . . . . . . . . . . . . . . . . . . . 48

C. Diammonium Tris(p-disulfido)tris(disulfido)-p3-thio- triangulo-trimolybdate(1V) Hydrate and Diammonium Bis(p-disulfido)-tetrakis(disulfido)dimolybdate(V)

10. Bis(q5-methylcyclopentadienyl)titanium Pentasulfide, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dihydrate 49

Bis( q 5-met h y lcyclopentadien y1)divanadium Pentasulfide, and Bis(~5-methylcyclopentadienyl)divanadium Tetrasulfide . . . . . 51 A. Methylcyclopentadiene.. . . . . . . . . . . . . . . . . . . . . . . . . . 52

Contents xv

B. Bis(qs-methylcyclopntadienyl)titanium Pentasullide . . . . C. Bis(qs-methylcyclopentadienyl)divanadium Pentasulfide . D. Bis(~~s-methylcyclopentadienyl)divanadium Tetrasulfide. .

1 1. Cyclometallapolysulfanes (and Selanes) of Bi~(tj-~-cyclopentadienyl) Titanium(IV), Zirconiurn(IV), Molybdenum(IV), and Tungsten(1V) . . . . . . . . . . . . . . . . . . . . A. Bis( q 5-cyclopentadienyl) [pentasulfido(2 - )]titanium( IV),

TiCp,S, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Bis(~5-cyclopentadienyl)[pentaselenido(2 -)]titanium(IV),

TiCp,Se, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Bis(tj-5-pentamethylcyclopentadienyl) [trisulfido(2 - )]-

titanium(IV), TiCp*,S3 . . . . . . . . . . . . . . . . . . . . . . . . . . D. Bis(qs-cyclopentadienyl)[tetrasulfido(2 -)]-

molybdenum(IV), MoCp, S,. . . . . . . . . . . . . . . . . . . . . . .

Titaniurn(1V) and Tungsten(1V). . . . . . . . . . . . . . . . . . . . . . . . A. Bis(q5-cyclopentadienyl)bis(hydrogensulfido)titanium(IV),

TiCp,(SH), . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Bis(qs-cyclopentadienyl)bis(hydrogensulfido)tungsten(IV),

WCp, (SH), . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (p-Disulfido-S)(p-disulfido-qz : $)Bis(q 5-pentarnet hyl- cyclopen tadienyl)(p-thio)dichromium( Cr- Cr) . . . . . . . . . . . . . .

12. Bisthydrogensulfido) Complexes of Bis(qs-cyclopentadienyl)

1 3.

Chapter Three EARLY TRANSITION METAL POLYOXOANIONS

14. Introduction to Early Transition Metal Polyoxoanions . . . . . 15. Tetrabutylammoniurn Isopolyoxometalates. . . . . . . . . . . . . . .

A. Tetrabutylarnmonium Hexamolybdate(V1). . . . . . . . . . . . B. Tetrabutylarnmonium Octamolybdate(V1) . . . . . . . . . . . . C. Tetrabutylarnmoniurn Dirnolybdate(V1). . . . . . . . . . . . . . D. Tetrabutylammoniurn Hexatungstate(V1). . . . . . . . . . . . . E. Tetrabutylarnmonium Decatungstate(V1). . . . . . . . . . . . . F. Tetrabutylarnmonium Trihydrogen Decavanadate(V) . . .

16. a-, fl-, and y-Dodecatungstosilicic Acids: Isomers and Related Lacunary Compounds . . . . . . . . . . . . . . . . . . . . . . . . A. Sodium a-Nonatungstosilicate, Na,,[a-SiW,O,,].solvent B. Sodium P-Nonatungstosilicate,

C. Potassium y-Decatungstosilicate, Na,[fl-SiW9O,,H]-23H,O . . . . . . . . . . . . . . . . . . . . . . .

K,[y-SiW 0036]. 12Hz0. . . . . . . . . . . . . . . . . . . . . . . . .

52 54 55

59

60

61

62

63

65

66

67

69

71 74 77 78 79 80 81 83

85 87

88

88

xv i Contents

D. Potassium a-Undecatungstosilicate,

E. Sodium p,-Undecatungstosilicate,

F. Potassium p,-Undecatungstosilicate,

G. Potassium 8,-Undecatungstosilicate,

H.

I.

J. Tetrabutylammonium y-Dodecatungstosilicate,

K, [a-SiW 03J - 1 3H , 0. . . . . . . . . . . . . . . . . . . . . . . . .

Na,[fi,-SiW , ,O,,].solvent . . . . . . . . . . . . . . . . . . . . . . .

Kg[fi2-SiWj 1039] .14H20. . . . . . . . . . . . . . . . . . . . . . . .

K,[p,-SiW,,0,,].14H20. . . . . . . . . . . . . . . . . . . . . . . . a-Dodecatungstosilicic Acid and Its Potassium Salt, H,[a-SiW 2040] . n H 2 0 and K,[a-Si W , 2040] . 17H,O. . fi-Dodecatungstosilicic Acid and Its Potassium Salt, H,[/?-SiW,,O,,].nH,O and K,[fi-SiW12040].9Hz0 . .

[(C,H,),N],[y-SiW 20,,] . . . . . . . . . . . . . . . . . . . . . . . 17. Vanadium(V) Substituted Dodecatungstophosphates . . . . . . .

A. P Chemical Shift Measurements of Tungstophosphates B. Tetrapotassium a-Vanadoundecatungstophosphate,

K,[a-PV'W, I 0 4 0 ] . x H 2 0 . . . . . . . . . . . . . . . . . . . . . . . . C. Nonasodium Nonatungstophosphate, Na,[A-PW,O,,] . D. Hexacesium a- 1,2,3-Trivanadononatungstophosphate,

E. Hexacesium Pentatungstodiphosphate, cs6[P2w,o23]

F. Pentacesium y-Divanadodecatungstophosphate,

G. Pentacesium fi-Divanadodecatungstophosphate,

18. Potassium Octadecatungstodiphosphates(V) and Related

cs6[~-1,2,3-PV,w90,0]. . e . . . . . . . . . . . . . . . . . v .

and Heptacesium Decatungstophosphate, Cs, [ PW , 0036]

cs , [y- PV, w

c s , [ p- PV , w 1 0 O,O]. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . .

Lacunary Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.

B.

C.

D.

E.

F.

Potassium-Octadecatungstodiphosphates, a Isomer:

K6[PZW18062]. 19H,O. . . . . . . . . . . . . . . . . . . . , . . . . . Potassium a,-Heptadecatungstodiphosphate, K o[az-P, W 0, , ] 20H , 0 . . . . . . . . . . . . . . . . . . . . . . Sodium a-Pentadecatungstodiphosphate,

Potassium r-Dodecatungstodiphosphate,

Potassium a, -Lithium Heptadecatungstodiphosphate,

Potassium Lithium Octatetracontatungstooctaphosphate, K,, Li,H7 [P,W,,O, ,,].92H,O . . . . . . . . . . . . . . . . . . .

K6[P,W,,O6,]* 14H2O; f i Isomer:

Na, 2 [a- P z w 5 O5,]'24H 2 0 . . . . . . . . . . . . . . . . . . . . . .

K 1 2 [z-H 2 P2 W 1 2 0 4 8 1 -24H 2 0 . . . . . . . . . . . . . . . . . . . . .

K9 [a -Li Pz w 7 0 6 1 ] ' 20H 0. . . . . . . . . . . . . . . . . . . . . .

89

90

91

92

93

94

95 96 98

99 100

100

101

102

103

1 04

105

107

108

108

109

110

Contents xvii

19. The Aquatrihexacontaoxobis[trioxoarsenato(III)]- henicosatungstate(6 - ) Anion Isolated as the Acid or as the Rubidium Salt. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Aquahexahydroxoheptapentacontaoxobis-

[trioxoarsenato(III)] henicosatungsten, H,[AS2 w2 1 0,,(H2 o)].nH2 0. . . . . . . . . . . . . . . . . . . . .

B. Tetrarubidium Aquadihydroxohenhexacontaoxobis- [trioxoarsenato(III)] henicosatungstate, H 2 Rb4 [AS, W 2 1 06,( H2 0)] .34H 2 0. . . . . . . . . . . . . . . . .

20. The Sodium Pentaphosphato(V)Triacontatungstate Anion Isolated as the Ammonium Salt . . . . . . . . . . . . . . . . . . . . . . .

21. Tetracontatungstotetraarsenate(II1) and Its Cobalt(I1) Complex A. Sodium Tetracontatungstotetraarsenate(III),

Na2, [NaAs, W4,0 140].60H20 . . . . . . . . . . . . . . . . . . . . B. Ammonium Tetracontatungstodicobaltotetraarsenate(III),

(NH~)~~[NH~AS~W~,O~~O(CO(H~O))~]*~~H~O. . . . . . . 22. Ammonium Sodium Henicosatungstononaantimonate(III),

23. Bis(p,-organophosphonato-0, 0’, 0)-penta-p-oxo- (NH4)1 ,[NaSb9W2,Os6]+24H20 . . . . . . . . . . . . . . . . . . . . . . . . . pentakis(dioxomolybdates, -tungstates)(4 - ) (Pentametallobisphosphonates) . . . . . . . . . . . . . . . . . . . . . . . . A. Pentamolybdobis(phosphonate). . . . . . . . . . . . . . . . . . . . B. Pentamolybdobis(methy1phosphonate). . . . . . . . . . . . . . . C. Pentamolybdobis(ethy1phosphonate) . . . . . . . . . . . . . . . . D. Pentamolybdobis(pheny1phosphonate). . . . . . . . . . . . . . . E. Pentamolybdobis[(Zaminoethyl)phosphonate] . . . . . . . . F. Pentamolybdobis[(p-aminobenzyl)phosphonate] . . . . . . . G. Pentatungstobis(pheny1phosphonate). , . . . . . . . . . . . . . .

trioxotitanate(1V)l-A-fl-1, 2,3- trivanadononatungstosilicate(4 - ), [ (C, H ,), N] [ A-fl-(q ,-C, H , )TiSi W , V , 04,] . . . . . . . . . . . . . . A. Hexapotassium Hydrogen A-fl-l,2,3-

24. Tetrakis(tetrabuty1ammonium) p,-[(qs-Cyclopentadienyl)-

trivanadononatungstosilicate(7 - ) Trihydrate, K6H[A-fl-SiW,V,0,,].3H20. . . . . . . . . . . . . . . . . . . . .

A-fl-l,2,3-trivanadononatungstosilicate(7 - ), [(C,H,),N]4H3[A-fl-SiW9V3040] . . . . . . . . . . . . . . . . .

trioxotitanate(IV)]-A-fl-1,2,3- trivanadononatungstosilicate(4 - ), [(C,H,),N], [A-fl-($--C, H s)TiSiW,V,040] . . . . . . . . . .

8. Tetrakis(tetrabuty1ammonium) Trihydrogen

C. Tetrakis(tetrabuty1ammonium) p3-[(qS-Cyclopentadienyl)-

1 1 1

112

113

115 118

118

119

120

123 123 124 125 125 126 126 127

128

129

131

132

xviii Contents

25 .

26 .

27 .

28 .

29 .

30 .

31 .

32 .

33 .

Chapter Four LANTHANIDE AND ACTINIDE COMPLEXES

Lanthanide Trichlorides by Reaction of Lanthanide Metals with Mercury(I1) Chloride in Tetrahydrofuran . . . . . . . . . . . . A . Ytterbium Trichloride-Tetrahydrofuran( 1/3) . . . . . . . . . . B . Erbium Trichloride-Tetrahydrofuran(2/7) . . . . . . . . . . . . C . Samarium Trichloride-Tetrahydrofuran( 1/2) . . . . . . . . . . D . Neodymium Trichloride-Tetrahydrofuran(2/3) . . . . . . . . Bis(phenylethynyl)ytterbium(II) from Ytterbium Metal and Bis(phenylethyny1)mercury . . . . . . . . . . . . . . . . . . . . . . . . . . . . A . Bis(phenylethynyl)ytterbium(II) ....................... Bis[bis(trimethylsilyl)amido]bis(diethyl ether)ytterbium and (Diethyl ether)bis(~s-pentamethylcyclopentadienyl)ytterbium . A . Ytterbium Diiodide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B . Bis[bis(trimethylsilyl)amido] bis(diethy1 ether)ytterbium . . C . (Diethyl ether)bis(~s-pentamethylcyclopentadienyl)-

ytterbium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cyclooctatetraene lanthanide Complexes . Lu(C,H, )Cl(thf) and

A . LU(C8 H,)Cl(thf) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lu(C,H, ) [o.C,H~CH,N(CH~), ] (thf) ....................

B . Lu(CSH,)[o.C,H4CH,N(CH,),](thf) . . . . . . . . . . . . . . . Bis(~’-pentamethylcyc1opentadienyl)bis(tetrahydrofuran)- samarium(I1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . tert-Butylbis(~s-cyclopentadienyl)( tetrahydrofuran)- neodymium ............................................ Bis(q5-cyclopentadienyl)(tetrahydrofuran)- [(trimethylsilyl)methyl]lutetium and Bis(qS-cyclopentadienyl)- (tetrahydrofuran)p.tolyllutetium ........................ A . Lu($.C, H5), [CH, Si(CH 3)3] (thf) . . . . . . . . . . . . . . . . . .

Hydrocarbon-Soluble Homoleptic Bulky Aryl Oxides of the Lanthanide Metals: [Ln(OArR),] . . . . . . . . . . . . . . . . . . . . . . . A . From a Lithium Aryl Oxide . . . . . . . . . . . . . . . . . . . . . . . B . From a Phenol ................................. Bis[qS- 1. 3-bis(trimethylsilyl)cyclopentadienyl]- chlorolanthanide(II1) Complexes. [ { LnCp”,(p.CI)}, ] and [LnCp”,(p.CI), Li(thf), ] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A . The Bis[$- 1.3.bis(trimethylsilyl)cyclopentadienyl 1.

di-p-chlorolanthanide(II1)-bis(tetrahydr0furan)- lithium Complexes. [LnCp”,(p.CI), Li(thf), ] . . . . . . . . . .

B . The Tetrakis[$- 1.3.bis(trimethylsilyl)cyclopentadienyl 1.

B . L u ( $ . C S H S ) ~ ( C ~ H ~ C H ~ . ~ ) ( ~ ~ ~ ) . . . . . . . . . . . . . . . . . . . . .

136 139 140 140 140

142 143

146 147 148

148

150 152 153

155

158

160 161 162

164 166 166

168

169

Contents xix

di-p-chlorodilanthanide(II1) Complexes, [ { LnCp”,(p- Cl)},]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

34. Bis[$- 1,3-bis( trimethylsil yl)cyclopentadienyl] halo- uranium(1V) and -Thorium(IV), [MCp”,Cl,] and [UCp”,X,] . A. Bis[qs-l, 3-bis(trimethylsilyl)cyclopentadienyl]-

dichlorothorium(1V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Bis[$-I, 3-bis(trimethylsilyl)cyclopentadienyl]-

dichlorouranium(1V). . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Bis[q5- 1,3-bis(trimethylsilyl)cyclopentadienyl]-

dibromouranium(1V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . D. Bis[q5- 1,3-bis(trimethylsilyl)cyclopentadienyl]-

diiodouranium(1V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35. Tris(q5-cyclopentadienyl)[(dimethylphenylphosphoranylidene)-

methylluranium(1V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Li(CH2)(CH,)P(CH3)(C6H~). . . . . . . . . . . . . . . . . . . . . . B. U(q5-C5H5)3[CHP(CH3)z(C6Hs)]. . . . . . . . . . . . . . . . . .

170

172

173

174

174

176

177 178 179

Chapter Five TRANSITION METAL CLUSTER COMPLEXES

36. Tetrairon Carbido Carbonyl Clusters . . . . . . . . . . . . . . . . . . . A. Bis(tetraethy1ammonium) Carbidohexadecacarbonyl-

hexaferrate(2 - ), (Et,N), [ Fe6(CO) 6c] . . . . . . . . . . . . . . B. Tetraethylammonium D o d e ~ a c a r b o n y 1 ~ ~ -

(methoxycarbonyl)methylidyne]tetraferrate( 1 - ), Et4N[Fe,(CO)1 ,C(CO,Me)] . . . . . . . . . . . . . . . . . . . . . . . . .

C. Carbidotridecacarbonyltetrairon, Fe,(CO), 3C . . . . . . . . . . D, Tetraethylammonium CarbidododecacarbonyIhydrido-

tetrafenat61 - ), Et4N[HFe,(CO)12C]. , . . . . . . . . . . . . . . . E. Bis(tetraethy1ammonium) Carbidododecacarbonyl-

tetraferrate(2 -), (Et4N)2[Fe4(CO)12C] , . . . . . . . . . . . . . 37. Tetraethylammonium Dodecacarbonyltricobaltferrate( 1 - )

and (Triphenylphosphine)gold( 1 + ) Dodecacarbonyl- tricobaltferrate(1 -) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Et,N[FeCo,(CO),,] . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Ph3 PAuFeCo3(CO), ,. . . . . . . . . . . . . . . . . . . . . . . . . . . .

38. Chiral Trinuclear NiCoMo and MoRuCo clusters . . . . . . . . . A. cyclo-p3-Ethylidyne-l :2:3dC-pentacarbonyl-

1 K~ C, 2dC-bis[ 1, 3(q5)cyclopentadienyl]cobaltmolyb- denumnickel(Co-Mo)(Co-Ni)(Mo- Ni), (p,-CH,C)NiCoMo(C, H5)2(C0)5 . . . . . . . . . . . . . . . . . .

182

183

184 185

186

187

188 188 1 90 191

192

xx Contents

1 . (~~.CH.C)CO.MO(C.H.)(CO). . . . . . . . . . . . . . . . . . 2 . (p3.CH.C)NiCoMo(C5H.).(C0). . . . . . . . . . . . . . . . cyclo.[p.. 1 (q'): 2(q2): 3(q2)-2-Butyne]octacarbonyl- 1 K' C. k3C. 3 ~ ~ C - c 1 (q 5)-cyclopentadienyl]cobalt- molybdenumruthenium(Co-Mo)(Co-Ru)(Mo-Ru).

B .

( ~ ~ - C ~ ( C H ~ ) ~ ) M O R U C O ( C ~ H.)(CO). . . . . . . . . . . . . . . . . 1 . (~~.C.(CH.).)RUCO,(CO). . . . . . . . . . . . . . . . . . . . . 2 . (/A~.C.(CH.).)MORUCO(C,H,)(CO). . . . . . . . . . . . . .

39 . Nonacarbonyl-tri-p-hydrido-p3-methylidyne-triruthenium and .osmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A .

B .

C .

D .

E .

F .

G .

H .

Decacarbony I-p- hydrido-p-( met hox y met hy1idyne)- triangulo-triruthrnium . . . . . . . . . . . . . . . . . . . . . . . . . . . Nonacarbonyl-tri-p-h~drid0-p~ -(met hoxymethy1idyne)- triangulo-trirut heni urn . . . . . . . . . . . . . . . . . . . . . . . . . . . p3-(Bromomethylidyne)-nonacarbonyl-tri-p-hydrido- triangulo-triruthenium . . . . . . . . . . . . . . . . . . . . . . . . . . . Decacarbonyl-p-h ydrido-p-(methoxymethy1idyne)- triangulo-triosmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nonacarbonyl-tri-p-hydrido-p3 -(methoxymet hy1idyne)- triangulo-triosmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nonacarbonyl-tri-p-h~drid0-p~- (methoxycarbonylmethylidyne).triangulo.triosmium . . . . . Nonacarbonyl-p3-(halomethy1idyne)-tri-p-hydrido- triangulo-t riosmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Decacarbonyl-di-p-hydrido-p-methylene-triangulo- triosmium and Its Hydridomethyl Tautomer . . . . . . . . . .

40 . Anionic and Heteronuclear Triosmium Clusters . . . . . . . . . . . A . Decacarbonyl-p-hydrido-p-[(triphenylphosphine)gold]-

triosmium and Decacarbonyl-p-hydrido-p- [(triethylphosphine)gold] triosmium . . . . . . . . . . . . . . . . .

B . Decacarbonylbis{p-[(triphenylphosphine)gold]}- triosmium and Decacarbonylbis{p- [ ftriethylphosphine)gold] } triosmium . . . . . . . . . . . . . . . .

pentapentacontagold. AuS5 [P(C,H,), ] 12C16 . . . . . . . . . . . . . . 41 . Hexachlorododecakis(tripheny1phosphine)-

A . Diborane(6) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

42 . A Platinum-Gold cluster: Chloro- 1 d'Lbis(triethy1phosphine- 11cP)bis(triphenylphosphine)-2~P, ~KP-triangulo- digoldplatinurn( 1 + ) Trifluoromethanesulfonate . . . . . . . . . . . A . AuCI(PPh, ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B . [PtCl{AuP(C,H,), j 2 { P(C,H,),}, ](CF3S03) . . . . . . . . .

B . A u ~ ~ [ P ( C ~ H ~ ) ~ ] ~ ~ C ~ ~ . . . . . . . . . . . . . . . . . . . . . . . . . . .

193 193

194 194 195

196

198

200

201

202

203

204

205

206 209

209

210

214 215 216

218 218 219

Conrents XXI

43 .

44 .

45 .

46 .

47 .

48 .

49 .

50 .

Chapter Six PHOSPHORUS COMPLEXES AND

Chloro(rt2-tetrahedro-tetraphosphorus)bis(triphenyIphosphine)- rhodium(I) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tetracarbonyl bis(t,?.cyclopentadienyl)(pq2.diphosphorus ). dimolybdenum(1) and Di~arbonyl(~~-cyclopentadienyl)- (q '-cycle- tri phosph or us)molybdenum( I) .................... Trilithium Heptaphosphide, Dilithiun Hexadecaphosphide. and Trisodium Henicosaphosphide ..................... A . Trilithium Heptaphosphide . . . . . . . . . . . . . . . . . . . . . . .

1 . Lithium Dihydrogen Phosphide . . . . . . . . . . . . . . . . .

COMPOUNDS

2 . Trilithium Heptaphosphide ....................... B . Dilithium Hexadecaphosphide ........................ C . Trisodium Henicosaphosphide .......................

Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I .Bromo.2,4,6.tri.ter t.butylbenzene . . . . . . . . . . . . . . . . . .

C . (2.4,6.tri.ter t.butylpheny1)phosphine . . . . . . . . . . . . . . . . . . D . (2,4,6.tri.ter t.butylphenyl)(trimethylsilyl)pho~phine . . . . .

Phosphorus Compounds Containing Sterically Demanding

A . B . (2,4,6.tri.ter t.butylphenyl)phosphonous dichloride . . . .

E . Tris(trimet hylsi1yl)methane ........................... F . [Tds(trimethylsilyl)methyl]phosphonous dichloride ..... Compounds with Unsupported P=P Bonds . . . . . . . . . . . . . . . A . Bis~tris(trimethylsily1)methyl~diphosphene and

BIs(2,4.6.tri.ter t.butylphenyl)diphosphene . . . . . . . . . . . . .

2 . Magnesium Method .............................

phosphide.bis(tetrahydrofuran) ........................... A . Tris(trimethylsily1)phosphine .........................

(2,2.Dimethylpropylidyne)phosphine . . . . . . . . . . . . . . . . . . . .

(trimethy1silyl)phosphine . . . . . . . . . . . . . . . . . . . . . . . . . . B . (2, 2.Dimethylpropylidyne)phosphine . . . . . . . . . . . . . . . . Triphosphenium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 . (Naphtha1ene)sodium Method ....................

Tris(trimethylsily1)phosphine and Lithium Bis(trimethylsily1)-

B . Lithium Bis(trimethylsilyl)phosphide.bis(tetrahydrofuran)

A . [Z, 2-Dimethyl- 1-(trimethytsiloxy)propylidenel-

A . 1,1, 1,3,3, 3-Hexaphenyltriphosphenium

B . 1.1,3,3.Tetraphenyl.l, 2.3-triphospholenyl

C . I , 1,1.3,3, 3.Hexakis(dimethylamino)triphosphenium

Tetrachloroalumina te . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Hexachlorostannate . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Tetraphenylborate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

222

224

227 228 228 230 232 233

235 236 236 237 238 238 239 240

241 241 242

243 243 248 249

250 251 253

254

255

256

xxii Contents

5 1. cis- 1,3-Di-rert-butyl-2,4-dichloro-l, 3,2,4- diazadiphosphetidine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Chapter Seven TRANSITION METAL COMPLEXES OF BIOLOGICAL INTEREST

52. Reversible Cobalt(I1) and Iron(I1) Dioxygen Carriers of Totally Synthetic Lacunar Cyclidene Complexes. . . . . . . . . . . . . . . . . A. A Lacunar Cyclidene Complex of Cobalt(I1) . . . . . . . . . .

1. [2,12-Dimethy1-3, I I -bis( 1 -methoxyethylidene)- 1,5,9,13-tetraazacyclohexadeca-l, 4,9,12-tetraene- ti4N1.5.9.13 ]nickel(II) Hexafluorophosphate, [Ni((MeOEthi),Me,[16]tetraeneN4)](PF,)2 . . . . . . . .

2. [2,12-Dirnethyl-3,11 -bis[l-(methylamino)ethylidene]- 1,5,9,13-tetraazacyclohexadeca-1,4,9,12-tetraene- ti4N1.5,9.13 ]nickel( 11) Hexafluorophosphate, (Ni((MeNHEthi),Me,[16]tetraeneN4)](PF,),. . . . . . .

3. (2,3,10,11,13,19-Hexamethyl-3,10,14,18,21,25- hexaazabicyclo[ 10.7.7]hexacosa-l1 1 1,13,18,20,25- hexaene-K4N14.1 8.21.15 )nickel(II) Hexafluorophosphate, [Ni((CH2),(MeNEthi),[l6]tetraeneN4)](PF6), . . . . .

hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25- hexaene] Hexafluorophosphate, [H,( (CH,),(MeNEthi), Me, [ 1 6]tetraeneN4)](PF6), .

hexaazabicyclo[l0.7.7jhexacosa-1,11,13,18,20,25- hexaene-h.4N14.18.21.25 )cobalt( I I) Hexafluorophos- phate, [Co( (CH,),( MeNEthi), [ 16]tetraeneN4)] (PF&

A Lacunar Cyclidene Complex of Iron(I1) . . . . . . . . . . . . . 1. [4,10-DimethyI-l, 5,9,13-tetraazacyclohexadeca-

4. [2,3,10,11,13,19-Hexamethyl-3,10,14, l8,21,25-

5. (2,3, 10, 11, 13,19-Hexamethyl-3,10,14,18,21,25-

B.

I , 3,9,1l-tetraenato(2 -)-~~N~*~.~~~~]nickel(II), [Ni(Me,[ 1 6JtetraenatoN4)]. . . . . . . . . . . . . . . . . . . .

tctraazacyclohexadeca- 1,3,9,11 -tetraenato(2 - )- K4N1.5.9,13 ]nickel(II), [Ni( Me,Bzyl,[1 6]tetraenatoN4)]. . . . . . . . . . . . . . . . . .

I , 5,9,13-tetraazacyclohexadeca- 1,4,9,12-tetraen-

[Ni((MeOBzi),Mc2[16]tctraeneN4)](PF,),. . . . . . . . .

2. [3,11 -Bis(benzoyl)-2, 12-dimethyl- 1,5,9,13-

3. [3,1 1-Bis(sc-methoxybenzylidene)-2,12-dimethyl-

k.4N 1.5.9. I 3 3 nickel( . 11) Hexafluorophosphate,

258

26 1 264

264

266

268

269

270 272

272

273

275

Contents xxiii

4. [3,11 -Bisfa-(benzylamino)benzylidene)-2,12-dimet hyl- 1,5,9,13-tetraazacyclohexadeca- 1,4,9,12- tetraene-~~N"'*~*~~]nickel(II) Hexafluorophosphate, [Ni((BzlNBzi),Me,[16]tetraeneN4)](PF6),. . . . . . . .

3,11,15,19,22,26-hexaazatricyclo[ 1 1.7.7.1 579]octacosa- 1,5,7,9(28), 12,14,19,21,26-nonaene- K ~ N ' 5~19.22~26]nickel(II) Hexafluorophosphate, [Ni((m-xylylene)(BzlNBzi), Me,[ 16]tetraeneN4)](PF6),

6. [3,ll-Dibenzyl-l4,20-dimethyl-2,12-diphenyl- 3,11,15,19,22,26-hexaazatricyclo[ 1 1.7.7.1 's9]-

octacosa- 1,5,7,9(28), 12,14,19,2 1,26-nonaene] Hexafluorophosphate, [ H ,((rn-xylylene)(BzlNBzi), Me, [ 1 6]tetraeneN4)](PF6),

7. [3,11-Dibenzyl-14,20-dimethyl-2,12-diphenyl- 3,11,15,19,22,26-hexaazatricycl0[11.7.7.1~~~]- octacosa-1,5,7,9(28), 12,14,19,21,26-nonaene- K ~ N ' '# ' 9.22r26]iron( 11) Hexafluorophosphate, [Fe( (m- xylylene)(BzlNBzi),Me,C 16]tetraeneN4)](PF6), . . . . .

53. [Pt( 1, 2-Cyclohexanediamine)(ascorbato-Cz, O')] . . . . . . . . . . A. [Pt(rrans-(R, R)-dach)I,] . . . . . . . . . . . . . . . . . . . . . . . . . . B. [Pt(trans-(R, R)-dach)(ascorbato-C', 0 ' ) ] . 3H20 . . . . . . . C. Modifications for cis-dach and trans-(S, S)-dach

Platinum Ascorbate Complexes . . . . . . . . . . . . . . . . . . . .

5. [3,1l-Dibenzyl-l4,20-dimethyl-2,12-diphenyl-

Chapter Eight MISCELLANEOUS TRANSITION METAL COMPLEXES

54. (Dithiocarbonato) [ 1, 1,l -tris(diphenylphosphinomethyl)ethane]- rhodium(II1) Tetraphenylborate Solvate . . . . . . . . . . . . . . . . .

55. The Vaska-Type Rhodium Complexes, trans-RhX(CO)L, . . . . A. Carbonyl(hydr0gen phthalato)bis(tricyclohexylphosphine)-

rhodium(1) .................................... B. Carbonyl( 1-methoxy-l13-butanedionato-O)bis-

(triisopropylphosphine)rhodium(I) . . . . . . . . . . . . . . . . . . 56. Potassium Hexaiodorhenate(1V) . . . . . . . . . . . . . . . . . . . . . . . 57. Group 6 Pentacarbonyl Acetates as Their p-Nitrido-

bis(triphenylphosphorus)( 1 + ) Salts . . . . . . . . . . . . . . . . . . . . . . . A. p-Nitrido-bis(triphenylphosphorus)(l +) Acetate. . . . . . . B. p-Nitrido-bis(triphenylphosphorus)( 1 + ) Pentacarbonyl

Acetato Group 6 Metal . . . . . . . . . . . . . . . . . . . . . . . . . .

276

277

278

280 283 284 284

284

287 290

29 1

292 294

295 296

297

xxiv Contents

58.

59.

60. 61. 62.

63.

64.

65. 66.

Bis(organoimid0) Complexes of Tungsten(V1) . . . . , . . . . . . . . A. Tetrachlorobis(1, 1-dimethylethanamine)bis[(l, 1-

dimethylethyl)imido] bis(pphenylimido)ditungsten(VI) . . . B. (2,2’-Bipyridine)dichloro[ (1,l -dimethylethyl)imido]-

(pheny1imido)t ungsten(V1) . . . . . . . . . . . . . . . . . . . . . . . . C. Dichloro[( 1, 1-dimethylethyl)imido](phenylimido)bis-

(trimethylphosphine)tungsten(VI) . . . . . . . . . . . . . . . . . . . Relatively Air-Stable M(I1) Saccharinates, M = V or Cr . . . . . A. Tetraaquabis( 1,2-Benzisothiazol-3(2H)-one 1,l-dioxidat0)-

vanadium(I1) Dihydrate . . . . . . . . . . . . . . . . . . , . . . B. Bis( 1,2-benzisothiazol-3(2H)-one 1, I-dioxidat0)tetrakis-

(pyridine)vanadium( 11)-Dipyridine . . . . . . . . . . . . . . . . . . . . C. Tetraaquabis( l12-benzisothiazol-3(2H)-one 1,l-dioxidat0)-

chromium(I1) Dihydrate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pyridinium Fluorotrioxochromate(VI), (C,H,NH)[CrO,F] . . Dipotassium Trifluorosulfatomanganate(II1). . . . . . . . . . . . . . . . cis-Dichlorobis( 1,2-ethanediamine)platinurn(IV) Chloride . . . . A. trans-Dichlorobis( 1 ,Zethanediamine monohydro-

chloride)platinum(II) . . . . . . . . . . . . . . . . . . . . . . B. cis-Dichlorobis( 1,2-ethanediamine)platinum(IV) Chloride Bis( 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)palladium and Its Complexes with 2,2’-Bipyridine and Bis[2-(diphenylphosphino)ethyl]phenylphosphine. . . . . . . . . . A. Bis( 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)palladium B. (2,2’-Bipyridine)(l, 1,1,5,5,5-hexafluoro-2,4-

pentanedionato)palladium(II) 1, 1, 1,5,5,5-hexafluoro- 2,4-dioxo-3-pentanide . . . . . . . . . . . . . . . . . . . . . . . . . . .

(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)palladium(II)- 1,1,1,5,5,5-hexafluoro-2,4-dioxo-3-pentanide. . . . . . . . .

C. [Bis[2-(diphenylphosphino)ethyl]phenylphosphine]-

Chapter Nine LIGANDS AND OTHER MAIN GROUP COMPOUNDS

Hybrid Tertiary Phosphine Amine and Amide Chelate Ligands: N-[2-(diphenylphosphino)phenyl]benzamide and 2-(Diphenylphosphino)-N-phenylbenzamide . . . . . . . . . . . . . . A. N-[2-(Diphenylphosphino)phenyl]benzarnide.. . . . . . . . . B. 2-(Diphenylphosphino)-N-phenylbenzamide.. . . . . . . . . . 1,1 -Dimethyl-N-(trimethy1silyl)ethanamine . . . . . . . . . . . . . . . . . Et h yn yl pen tafluoro-A6-sulfane (S F , C= CH) . . . . . . . . . . . . . . . .

300

30 1

303

304 306

307

308

309 310 312 3 14

315 316

317 318

3 19

320

322 323 324 327 329

Contents xxv

A. SF,CH=CHBr .................................... B. SF,C-CH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

67. Iodine and Bromine Polysulfur Hexafluoroarsenate(V) and Hexafluoroantimonate(V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Iodo-cyclo-heptasulfur Hexafluoroarsenate(V),

[S,I] [ASF,] and iodo-cyclo-heptasulfur Hexafluoroantimonate(V), [S, I] [SbF,] . . . . . . . . . . . . . .

antimonate) Bis(arsenic trifluoride), B. p-Iodo-bis(4-iodo-cyclo-heptasulfur) Tris(hexafluoro-

[(S,I)ZI] [SbF6],.2ASF,. . . . . . . . . . . . . . . . . . . . . . . . . . C. Bromo-cyclo-heptasulfur Hexafluoroarsenate(V),

[S,Br] [ASF,] and Bromo-cyclo-heptasulfur hexafluoroantimonate(V), [S,Br] [SbF6] . . . . . . . . . . . . .

Containing the Iodo-cyclo-heptasulfur( 1 + ), Bromo-cyclo- heptasulfur( 1 +), and Tetrasulfur(2 +) Cations. . . . . . . . .

Trimethylborane.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

D* [(s71)4s41 CAsF616 and [(S7Br)4S41 CAsF6l6

68.

Sources of Chemicals and Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . Index of Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Subject Index.. . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . Formula Index. . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

330 330

332

333

335

336

337 339

343

345

35 1

373

INORGANIC SYNTHESES

Volume 27