Synthetic Methods of Organometallic andInorganic Chemistry(Hellmann/Brauer)

Edited by Wolfgang A. Herrmann

Synthetic Methods of Organometallic andInorganic Chemistry(Herrmann/Brauer)

Volume 3Phosphorus, Arsenic, Antimony, andBismuth

Volume Editor: H. H. Karsch

30 Figures, 17 Tables

Georg Thieme Verlag Stuttgart • New York 1996

Prof. Dr. rer. nat. Wolfgang A. Herrmann

Anorganisch-chemisches Institut der

Technischen Universitat MtinchenLichtenbergstral3e 4

D-85747 Garching bei Munchen

Prof. Dr. rer. nat. Hans H. KarschAnorganisch-chemisches Institut derTechnischen Universitat Mtinchen

Lichtenbergstrahe 4

D-85747 Garching bei Mtinchen

Library of Congress Cataloging- in-Publication Data

Synthetic methods of organometallic and inorganic chemistry / editedby Wolfgang A. Herrmann

p. cm.

Includes bibliographical references and indexes

Contents: Phosphorus, Arsenic, Antimony, and Bismuth /

volume editor, H. H. Karsch

ISBN 3-13-103041-0 (GTV). ISBN 0-86577-654-7 (TMP)

1. Organometallic compound--Synthesis. 2. Inorganic compounds--Synthesis. Karsch, H. H.

QD411.S96 1996541.39--dc20 95-49908

CIP

Die Deutsche Bibliothek — C1P-Einheitsaufnahme

Synthetic methods of organometallic and inorganic chemistry /

(Herrmann/Brauer). Ed. by Wolfgang A. Herrmann. - Stuttgart;New York : ThiemeNE: Herrmann, Wolfgang A. [Hrsg.]

Vol. 3. Phosphorus, Arsenic, Antimony, and Bismuth /vol. ed.: H. H. Karsch. - 1996NE: Karsch, Hans Heinz [Hrsg.]

Some of the product names, patents and registered designs referred to in this book are in fact registered trademarks or

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Georg Thieme Verlag, Stuttgart Thieme Medical Publishers, Inc., New YorkISBN 313 103041 0

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Preface to the SeriesSynthetic Methods of Organometallic and Inorganic Chemistry

It was the German chemist Ludwig Vanino 1 (1861 — 1941) (Figs. 1 and 3) who wrote the famous Handbuch derPraparativen Chemie (Handbook of Synthetic Chemistry). This book became well known in all chemical labo-ratories of the time. It contained a comprehensive collection of standard inorganic and organic laboratory proce-dures compiled in one volume and was originally intended to support practical courses inAdolf von Baeyer'slaboratory in Munich (Fig. 3). When the third edition of the "Vanino" went out of print in the year of 1940, theFerdinand Enke publishing company (Stuttgart, Germany) developed a new concept in which procedures for thepreparation of scientifically interesting and didactically important inorganic compounds were compiled. Themain emphasis was placed on the reliability and reproducibility of the reported procedures.

Figure 1 Ludwig Vanino, the editor of the "Hand-buch der Praparativen Chemie". After receiving hisdoctor's degree at the University of Erlangen in1891, Vanino became a co-worker of Hans vonPechmann (Munich) and was later (1911) awardedthe title of a "KOniglicher Professor" (Bavarian RoyalProfessor).

Figure 2 Professor Georg Brauer (1908 —), thefounder of the "Handbuch der Praparativen Anor-ganischen Chemie" bearing his name since 1954.

Figure 3 The "Anorganische Abteilung" of the Munich chemistry laboratory under the direc-tion of Adolf von Baeyer (front row, middle) during the summer semester of 1898. LudwigVanino is in the second row (third from the left).

Ber. dtsch. chem. Ges. 74, A232 (1941); Chem.-Ztg. 65, 402 (1941).

vi Preface to the Series

As a result of World War II, the first edition of the newHandbuch der Preiparativen Anorganischen Chemie didnot appear until 1954. Georg Brauer (1908 — ) (Fig. 2), a professor of inorganic chemistry at the University ofFreiburg (Germany), merits respect not only for having started the new"Handbuch" in difficult times but alsofor creating a standard book of chemical recipes which became famous throughout the world in spite of beingpublished in German. The third edition, meanwhile expanded to three volumes, was completed in 1981. On thatoccasion, organometallic compounds were included for the first time as a separate chapter (W. P. Fehlhammer,W. A. Herrmann, K. Ofele: Metallorganische Komplexverbindungen) in the third volume to cope with the enor-mous growth experienced by this class of compounds in the years following publication of the first edition, asexemplified by two milestones, the discovery of ferrocene in 1951/1952 and dibenzenechromium in 1955.

The special and wide-ranging influence of organometallic chemistry upon chemical science in general andthe necessity for the worthy successor to Vanino and Brauer has required a new conception as well as the publi-cation of "Synthetic Methods of Organometallic and Inorganic Chemistry" in English. A total of eight volumesare planned to cover the most important standard compounds that appear to be in general use in laboratories en-gaged in all branches of synthetic chemistry. In most cases, no strict borderline has been drawn between inor-ganic and organometallic compounds. Instead, we have attempted to keep up with the developments in coordi-nation and organometallic chemistry, areas which were underrepresented in the previous first (1954), second(1960), and third (1975 — 1981) editions of Brauer. The material is presented in such a way that, for every groupof elements, the various aspects of the chemistry are combined. The following volumes are planned for theseries (the names of the volume editors are given in parentheses):

Volume 1

Volume 2Volume 3Volume 4Volume 5

Volume 6Volume 7Volume 8

Literature, Laboratory Techniques, and Common Starting Materials(W. A. Herrmann/A. Salzer)Groups 1, 2, 13, and 14 (N. Auner/U. Klingebiel)Phosphorus, Arsenic, Antimony, and Bismuth (H. H. Karsch)Sulfur, Selenium, and Tellurium (K I Irgolic/N.N.)Copper, Silver, Gold, Zinc, Cadmium, and Mercury (D. Breitinger/W. A.Herrmann/W. Hiller)Lanthanides and Actinides (F. Edelmann)Transition Metals, Part 1 (W. A. Herrmann/F. R. Krei131)Transition Metals, Part 2 (W. A. Herrmann/F. R. KreiJ31)

In view of the enormous growth of organometallic chemistry, particularly in the past 20 years, the editorswere faced with the difficult task of selecting typical compounds in general use and thus no claims of a compre-hensive and complete coverage can be made. However, the user of this recipe book may expect— and will hope --fully find — a balanced selection of older and newer examples of all classes of compOunds with detailed and re-liable experimental procedures in the eight volumes of this series. Separated from each other since the days ofLudwig Vanino, organic aspects have once again been integrated into inorganic chemistry.

The series editor gratefully acknowledges the help of numerous colleagues who have acted as volume editorsand donated their expertise in their respective fields or who have contributed well-proven preparations. It mustbe emphasized, however, that neither the editors nor the contributors can undertake any liability for problemsresulting from any of the given procedures. It is the responsibility of every laboratory worker to take all precau-tions necessary to ensure his/her safety and the safety of all others in the vicinity.

The editor is also indebted to Dr. Joe P. Richmond of Georg Thieme Verlag and Dr. Richard Dunmur, thedesk editor, for their patient and competent help in the preparation of this balanced and well-organized newhandbook series. Furthermore, the technical assistance of Dr. Florian Dyckhoff and Mr. Thomas Dambacher ismuch appreciated.

Garching, November 1995 Wolfgang A. HerrmannTechnische Universitat Munchen

(a) T. J. Kealey, P. L. Pauson, Nature 168, 1039 (1951).(b) S. A. Miller, J. A. Tebboth, J. F. Tremaine, J. Chem. Soc. (fondon) 632 (1952).E. O. Fischer, W. Hafner, Z. Naturforsch. 10b, 665 (1955).

Preface to Volume 3

The present volume was originally conceived as a single chapter within the planned two-volume workdescribing modern synthetic procedures for organoelement compounds. However, the overwhelmingresonance and the participation of so many authors led to the present eight-volume series. The responsefrom the authors in the field of group 15 element chemistry was particulary large and numerous leadingexperts accepted our invitation and contributed a plethora of high-quality synthetic procedures, most ofwhich will be extremely useful and of major topical interest since they describe the "heart" of thecurrent research in the respective laboratories. As a consequence, this third volume in the series"Synthetic Methods of Inorganic and Organometallic Chemistry" is dedicated to group 15 elementcompounds and is completely composed of contributions from individual research groups. Theparticipation of these distinguished authors donates a personal character to the individual parts andguarantees the highest possible expertise.

Quite naturally, this change in the concept also involved considerably more time for its realizationthan was originally planned as well as more editorial work to achieve our objective of creating acomprehensive, concise, and competent collection of procedures for Herrmann/Brauer. Thus, I amdeeply indebted to the authors of this volume for contributing their experiences as well as for theirpatience and tolerance in the light of all the inquiries, inevitable corrections, suggestions, changes, andadditions during the preparation of this book. We all hope that this volume will become anindispensible tool for advanced students and research workers in university and industrial laboratories.

I also thank all the members of my own team for their valuable help with the editorial workincluding corrections and reorganization of the manuscripts. Special thanks are due to Roland Richteras the main contributor to this enthusiastic team. I am further indebted to Dr. Richard Dunmur, thedesk editor, who checked each text carefully and arranged them in a consistent manner, to Dr. FlorianDyckhoff for some assistance with the electronic preparation of formulae, and to Professor WolfgangHerrmann for general support.

Garching, February 1996 Hans H. KarschTechnische Universitat Munchen

List of Abbreviations

1-Ad or Ad-(1) adamant-1-y] kg kilogramAr aromatic or aryl L literAr* 2,4,6-tri-tert.-butylphenyl (supermesityl) liq. liquidby boiling point m- meta-bph 4,4',5,5 1 -tetramethy1-2,2'-biphosphinine m meter or multiplet (NMR)br broad M molarBu butyl Me methylt-Bu (or Bu-t) tertiary butyl Me3 Si trimethylsilylcat. catalyst Mes 2,4,6-trimethylphenyl (mesityl)cm centimeter mL milliliterC4Me4N tetramethylpyrrolyl mm millimeterCp cyclopentadienyl mp melting pointCp* pentamethylcyclopentadienyl MS mass spectrum or mass spectroscopyd doublet n- normalDBN 1,5-diazabicyclo[4.3.0]non-5-ene N normal (concentration)DBU 1 ,8-diazabicyclo[4.4.0]undec-7-ene nm nanometerdd double doublet NMR nuclear magnetic resonancedec. decomposition o- ortho-diglyme bis(2-methoxyethyl) ether (ethylene P- para-

glycol dimethyl ether) Ph phenylDME 1 ,2-dimethoxyethane Pr propylDMF dimethylformamide q quartetDMSO dimethyl sulfoxide second or singlet (NMR)dq double quartet s- or sec.- secondarydt double triplet sept septetEt ethyl t- or tert.- tertiaryeV electron volt THF tetrahydrofuranFVP flash vacuum pyrolysis TMEDA tetramethylethylenediamine or 1,2-FVT flash vacuum thermoylsis bis(dimethylamino)ethaneg TMS tetramethylsilanegramh hour tppts trisodium triphenylphosphanesulfonatei-Pr (or Pr-i)IR

isopropylinfrared

UV ultraviolet

Contents

Chapter 1IntroductionHans. H Karsch 1

Chapter 2Acyclic Phosphorus(III) Compounds 6

2.1 Coordination Number 1 7Methylidynephosphane

P. Le Floch, F. Mathey 8(2,2-Di methylpropyl idyne)phosphane, (Adamant-l-yl-methylidyne)phosphane

W. Nisch, T. Allspach, U Bergstrafler, M Regitz 11

Bis(1,2-dimethoxyethane-0, 0 ')lithoxymethylidynephosphane, Tris(1,2-dimethoxyethane-0,0)lithium27,,3 -PhosphaethynylsulfanideG. Becker, K. flabler, 0. Mundt, N. Seidler 16

(2,4,6-Tri-tert.-butylphenyl)phosphatriylammonium TetrachloroaluminateE. Niecke, V von der Gonna, M Larbig 20

Group 15 Carbene Analogues: Cationic Bis(amino)phosphenium and -arsenium CompoundsN. Burford, J. A. C. Clyburne, P. Losier, T. M Parks 21

2.2 Coordination Number 2 27

Chloro(2,4,6-tri-tert.-butylphenyl)iminophosphaneE. Niecke, J. Hombeuel, M. Blattner, V. von der Gonna, A. Ruban 28

Dichloromethylene(2,4,6-tri-tert.-butylphenyl)phosphaneE. Niecke, F. Baumeister 30

1-Bromo-2-phenyl-2-trimethylsi ly1-1-phosphaetheneE. Niecke, R. Pietschnig 33

2,2-B i s(trim ethyls i ly1)-1-ch lorophosphaetheneE. Niecke, D. Schmidt 34

[Bis(trimethylsilypamino]trimethylsilyliminophosphaneE. Niecke, R. Oberdorfer, V Bajorat 36

Di-tert-butylcarboimidophosphene0. 1. Kolodiazhnyi 37

(Z)4(Chloro)(lithio)methylenel(2,4,6-tri-tert.-butylphenyl)phosphane and its Derivatives: (Z)-

[(tert-Butylcarbonyl)(chloro)methylene](2,4,6-tri-tert.-butylphenyl)phosphane, (Z)-[(Chloro)(trimethylsiloxycarbonyl)methylene]-2,4,6-tri-tert-butylphenyl)phosphane,(Z)-Rcarboxy)(chloro)methylene1(2,4,6-tri-tert.-butylphenyl)phosphaneF. Bickelhaupt, M von der Sluis 39

2,2-Di methy1-1-(trimethylsiloxy)propylidene(trimethylsilyl)phosphane, Adamant-l-y1-(trimethylsiloxy)methylidene(trimethylsily0phosphaneW. RO.sch, T. Allspach, U Bergstrager, M Regitz 41

(2,3-Di-tert. -butylcyclopropen-l-ylidene)mesitylphosphane, (2,3-Di-tert.-butylcyclopropen-l-ylidene)-

(trimethylsi lyl)phosphane, (2,3-Di-tert. -butylcyclopropen-l-ylidene)pivaloylphosphane

W. Eisfeld, E. Fuchs, M Regitz 44

Further Acyclic X3 ,o2-Phosphorus Compounds 47

2.3 Coordination Number 3 48

Primary A lkylphosphanesF. Uhlig, E. Herrmann 48

Chloromethyldichlorophosphane Sulfide, ChloromethyldichlorophosphaneK. Karasghiosoff, A. Schmidpeter, P. Mayer 52

x

tert.-Butyldichlorophosphane, Dichloro(isopropyl)phosphaneK. Karaghiosoff K. Eckstein 54

Bis(trimethylsilyI)(diisopropylamino)phosphane, Chloro(diisopropylamino)trimethylsilylphosphaneE. Niecke, V. von der Gonna, M Larbig 57

Tris(trimethylsilyl)phosphane, Alkylbis(trimethylsilyl)phosphanes, Bis(alkyl)(trimethylsily1)-phosphanes, Sodium Bis(trimethylsilyl)phosphide, Potassium Bis(trimethylsilyl)phosphideH. H. Karsch, F. Bienlein, T. Rupprich, F. Uhlig, E. Herrmann, M Scheer 58

Dialkyl(fluoro)silylphosphanes, Silanediylbisphosphanes, Alkali Metal (Dialkylfluorosilyl)phosphides,Bis(dialkylfluorosilyl)phosphanes, Diphosphadisilacyclobutanes, TriphosphasilacyclobutanesU. Klingebiel 65

Bis(trimethylsilyI)-tert.-butylphosphaneO. I. Kolodiazhnyi 70

Bis(methoxycarbonyl)methyl(sec. -butyl)(tert. -butyl)phosphaneO. I. Kolodiazhnyi 71

Bis(dimethylamino)chlorophosphane, (2-Bromophenyl)dichlorophosphane, Bis(dimethylamino)-(2-bromophenyl)phosphane, 1,2-Bis(dimethylaminophosphanyl)benzeneJ. Thomaier, H. Griitzmacher 73

Dichloro(tetramethylpyrrolyl)phosphane, Bis(tetramethylpyrrolyl)chlorophosphane,Tris(tetramethylpyrrolyl)phosphane, 1,1,2,2-Tetrakis(tetramethylpyrrolyl)diphosphane,Tetrakis(tetramethylpyrrolyl)cyclotetraphosphane

N. Kuhn, K. Jendral 76

Further Acyclic X3 ,63 -Phosphorus Compounds 79

Chapter 3Acyclic Phosphorus(V) Compounds 80

3.1 Coordination Number 3 81

2,4,6-Tri-tert. -butylphenyldithioxophosphoraneE. Niecke, R. Serwas 81

Bis[bis(trimethylsilypmethylene](chloro)phosphoraneE. Niecke, P. Becker, K Paasch, P. Wenderoth 82

[Bis(trimethylsilyl)amino]bis(trimethylsilylimino)phosphoraneE. Niecke, R. Oberdôrfer, V. Bajorat 84

3.2 Coordination Number 4 85

(Chloro)(di-tert.-butyl)phosphane, (Di-tert.-butyl)(diphenylmethyl)phosphane, [(Chloro)(di-tert.-buty1)-phosphoranylideneidiphenylmethane, 1,1-Di-tert.-butyl-2,2-diphenylmethylenephosphoniumTetrachloroaluminateH. Grutzmacher 85

Chloro(di-tert.-butyl)phosphoniummethylideO. I Kolodiazhnyi 88

DiethylaminodifluorophosphoniumbutylideO. I Kolodiazhnyi 91

(Di-tert.-butylthiophosphinoy1)(isopropyl)thioketeneO. I. Kolodiazhnyi 92

(Di-tert.-butylphosphinoy1)(methyl)keteneO. I Kolodiazhnyi 94

(Diethylphosphono)(phenyl)keteneO.I.Kolodiazhnyi 95

Diphenylbis(phenylsulfonyl)methylphosphane OxideO. I Kolodiazhnyi 97

x i

(Triphenylphosphoranylidene)methane, (Triphenylphosphoranylidene)bis(trimethylsily1)-methane, [Tris(dimethylamino)phosphoranylidene]methaneH Grutzmacher 99

N,N-Bis(trimethylsilyl)amino(diphenyl)phosphane, (Chloro)(diphenyl)(N-trimethylsilyl-imino)phosphorane, /V,N-Bis(trimethylsilylamino)(diphenyl)(N-trimethylsilylimino)-phosphoraneM Witt, H W. Roesky 103

Further Acyclic X5 ,64-Phosphorus Compounds 105

Chapter 4Acyclic Compounds Containing Two or More Phosphorus Atoms 106

Lithium Dimethylphosphanomethanide, Bis(dimethylphosphano)methaneH H Karsch 107

Dichloro(diisopropylamino)phosphane, Dichloro(diphenylamino)phosphane,1,2-B is(d i isopropylam ino)-1,2-dichlorodiphosphaneK Karaghiosoff S. Soheili 110

Pentamethylcyclopentadienyl-Substituted Phosphanes, Diphosphanes, Cyclophosphanes,1,2-Diphosphaseleniranes, DiphosphenesP. Jutzi, N. Brusdeilins, A. Mix 113

2,4,6-Tri-tert.-butylphenylphosphane, (E)-1,2-Bis(2,4,6-tri-tert.-butylphenyl)diphosphene,(E)-1-(2,4,6-Trimethylpheny1)-2-(2,4,6-tri-tert. -butylphenyl)d i phospheneM Yoshifuji 118

Bis(trimethylsilyl)phosphido(dicarbonyl)(pentamethylcyclopentadienypiron, (E)-1-[Dicarbonyl-(pentamethylcyclopentadienyl)ferriol-242,4,6-tri-tert.-butylphenyl]diphospheneL. Weber, K. Reizig 125

Diphosphiranes, Diphosphapropenes, DiphosphaallenesG. Etemad-Moghadam, M Gouygou, C. Tachon, M Koenig 128

1,3-Bis(2,4,6-tri-tert.-butylpheny1)-1,3-diphosphaallene and its Precursors: BisRchloro)(2,4,6-tri-tert.-butylphenyl)phosphano]methane, (E)-1,3-Bis(2,4,6-tri-tert.-butylpheny1)-3-chloro-1,3-diphospha-propeneH H Karsch, H. Reisacher, T Rupprich 140

A Lithium Diphosphaallyl Anion and its PrecursorH H Karsch, H Reisacher, A. Schneider, T. Rupprich 143

Dichlorophosphano(tolyl)methylene(triphenyl)phosphorane, Dichlorophosphano(ethyl)-methylene(triphenyl)phosphoraneG. Jochem, A. Schmidtpeter 147

[Chloro(triphenylphosphoranylidene)methyl]triphenylphosphonium Chloride,HexaphenylcarbodiphosphoraneH Grutzmacher 150

1,1,1,3,3,3-Hexaphenyltriphosphenium Tetrachloroaluminate, 1,1,1,3,3,3-Hexakis-(dimethylamino)triphosphenium TetraphenylborateA. Schmidtpeter 153

Further Acyclic Phosphorus Compounds Containing Two or More Phosphorus Atoms. 155

Chapter 5Mono- and Polycyclic Phosphorus Compounds 156

3-tert.-Butyl-1-chloro-2-pheny1-1H-phosphireneR. Armbrust, O. Wagner, M. Regitz 157

2,2,4,4-Tetrakis(diisopropylamino)-1,3,2X 5 ,4X5 -diazadiphospheteA. Baceiredo, J. Majoral, G. Bertrand 160

xii

1,2,4-Diazaphosphole and its Precursor 1,3-Bis(dimethylamino)-2-phosphaallylic ChlorideA. Schmidtpeter 162

1,1',3,3'-Tetrakis(dimethylamino)-1A. 5 ,3k5 -diphosphete, 1,1',3,3',5,5'-Hexakis(dimethyl-am ino)-17< 5 ,3 k5 ,5k5 -triphosphabenzeneE. Fluck, G. Heckmann 165

4,4',5,5'-Tetramethyl-2,2'-biphosphinine, cis-[Dichlorobis(4,4',5,5'-tetramethy1-2,2'-biphosphinine)ruthenium(INP. Le Floch, D. Carmichael, F. Mathey 167

2,4,6,8-Tetra-tert. -butyl-1,3 ,5,7-tetraphosphapentacyclo[4.2.0.0 2,5 .03,8 .04,7]octaneT. Wettling, B. Geissler, M. Regitz, P. Binger 172

Bis(r1 5 -cyclopentadieny1){2,4-di-tert.-buty1-1,3-diphosphabicyclo[1.1.0]butane-2,4-diyll zirconiumP. Binger, B. Biedenbach, S. Leininger, M Regitz 175

Synthesis of Exceedingly Strong Non-Ionic Bases Based on 2,8,9-Trimethy1-2,5,8,9-tetraaza-1-phosphabicyclo[3 .3.3]undecaneJ. Tang, J. G. Verkade 177

Synthesis of Pentaoxyphosphoranes with Sulfur-Containing Eight-Membered RingsT. K. Prakasha, R. R. Holmes 181

Further Mono- and Polycyclic Phosphorus Compounds 187

Chapter 6Compounds of Arsenic, Antimony, and Bismuth 188

Arsane, (1,2-Dimethoxyethane-0,0')lithium Arsanide, [1,2-Bis(dimethylamino)ethane-NY] lithium ArsanideG. Becker, D. Kiishammer, O. Mundt, M. Westerhausen 189

Tris(trimethylsilylarsane), -stibane, -bismuthane, (1,2-Dimethoxyethane-0,0')IithiumBis(trimethylsilyl)arsanide, -stibanide, -bismuthanideG. Becker, H. Freudenblum, O. Mundt, M Reti, M Sachs 193

Diiodo(methyl)arsane (Methylarsenic diiodide)R. A. Zingaro 198

TriethylarsaneR. A. Zingaro 200

Trimethylarsane OxideR. A. Zingaro 202

Dimethylantimony Bromide, Methylantimony DibromideH. J. Breunig, M Ates, M Denker, K. H. Ebert 203

Triethylstibane, Triethylantimony Dibromide, Diethylantimony Bromide, EthylantimonyDibromide, Ethylantimony Polymer, Pentaethylcyclopentastibane,TetraethylcyclotetrastibaneH. J. Breunig, M Ates, S. Gulec, K H. Ebert 205

Trimesitylstibane, Mesitylantimony Dibromide, Tetramesitylcyclotetrastibane • TolueneH. I Breunig, M Ates, A. Soltani-Neshan, K. H. Ebert 208

Dihalo(phenyl)stibanes, Dihalo(phenyl)bismuthanesG. Becker, J. Egner, O. Mundt, H. Stadelmann 210

Further Compounds of Arsenic, Antimony, and Bismuth 214

Subject Index 215

Formula Index 223

Chapter 1 Introduction

Hans H. KarschAnorganisch-chemisches Institut, Technische Universitat Munchen, LichtenbergstraBe 4, D-85747 Garching, Germany

2 1 Introduction

The first elementorganic compound to be synthesized was Me2AsAsMe2 described by Cadet in 1760.In elementorganic chemistry ever since, the group 15 elements represent one of the most fruitful andprospering fields. This is not only due to the high importance of these compounds with their applica-tions in medicine, biology, agriculture, organic synthesis, and many other industrial fields but also totheir structural variety. With phosphorus as the dominating element in this series as an example,coordination numbers ranging from 1 to 7, oxidation states from –3 to +5, and bond multiplicities from1 to 3 are found and most of these features also arise in its organic derivatives. Furthermore, the ver-satility of this element and its compounds, e.g. the NMR properties of the 31 P nucleus on the one handand the widespread use of organophosphorus compounds as ligands in transition metal chemistry andhence, catalysis, on the other hand, make the chemistry of organophosphorus compounds important toa wide range of chemists — from theoreticians to applied chemists. In this respect, among all the otherelements, phosphorus is rivaled only by carbon. Both elements are connected by a diadic relationshipin the periodic table, which donates specific significance to compounds with a phosphorus to carbonbond. And last but not least, the chemistry of organophosphorus compounds is a fascinating challengeto the experimental chemist — the synthesis of most of these compounds requires tricky methods andexperimental skill — and this is reflected in the ultimate goal of the present volume: the presentation ofexamples for the detailed, competent, and reliable description of the synthesis of the compoundsnowadays involved in elementorganic chemistry of group 15 elements — either as valuable intermedi-ates or even as a constituent of actual research. This aim only can be reached by the concentrated ef-forts of leading experts in the respective fields. In fact, this volume differs from all others in the seriesin that it includes only original material from experienced authors, i.e. procedures thoroughly tested intheir own laboratories and relevant to their ongoing research work. This criterion certainly has"disadvantages": it does not result in a completely uniform appearance and style of the contributionsand does not cover the whole spectrum of possible organoelement compounds uniformly. But in a jointeffort, a high degree of consistency within a very broad range has been established.

In the selection process of useful procedures, main emphasis was focused on the synthesis of valu-able starting compounds, i.e. functionalized phosphanes and — in relation to their importance to alesser degree — the higher congeners. The majority of these procedures has not been described previ-ously in a detailed manner As a result of the progress in the availability of unsaturated organophos-phorus species, the synthesis of multiple bonded species also is considered with numerous examples.Many of the compounds included here have only recently been described in original papers and are ofhigh interest for actual research work. This part includes neutral and cationic, cyclic and acyclic, dou-ble and triple bonded, conjugated and cumulated compounds as well as some very special examples. Inaddition, cationic phosphenium type structures, cyclic and acyclic, formally derived from P(III) andP(I), are also described. Likewise, numerous phosphorus ylides with various substituents, somephosphorus oxides and sulfides, a number of compounds containing P–P bonds, as well as rings andeven cages, and, in addition, some hypervalent species are included with representative examples.

To achieve the aim of covering a broad and significant area, also compounds not containing a phos-phorus-carbon bond but which are of specific interest in this context (either in their own right or asvaluable starting materials) are included. It was also attempted to cover a broad field of different meth-ods: from one-pot syntheses to multistep procedures, from the usual addition-stirring-filtration-distilla-tion routine to more sophisticated methods including ultrasound and photochemical reactions. Al-though the latter methods are not readily available in a course for undergraduate students, they tracethe path for further developments in preparative chemistry and may be useful for the research activitiesof graduate students and of post-doctoral research workers in university or industrial laboratories.

1 Introduction 3

With the intention of providing a high level of information and validity and hence ensuring an op-timized value for the reader, the synthetic potential of the individual class of compounds is describedas an introductory part of each contribution.

Within a broadly growing field of research, parallel developments are quite common. This is alsotrue for the elementorganic chemistry described in this volume. Therefore, very often several differentmethods for the synthesis of a given class of compounds have been devised. These different methodsare listed, and in most cases, comments are given to enable the reader to make an individual choice.The different methods reflect the availability of starting materials as well as the specific knowledgeand experience of the respective laboratory. In general, in this volume, only one — the apparently bestsuited — synthetic procedure for a specific compound is described in detail. In certain cases, however,where a "best" method cannot readily be distinguished, several independent routes are considered. Thisis intended not only to illuminate the above-mentioned trend and the specific potentials of the diverselaboratories, but also to provide valuable synthetic alternatives for some important compounds andthus enhance the practical value of this part.

The source of reagents needed, the hazards and necessary precautions, as well as the properties aredescribed in detail. Since risks in the handling of organophosphorus compounds are often not known indetail, caution has to be applied in practically all cases even though appropriate notes have only beengiven for a restricted number of the procedures. Gloves and eye/face protection should be worn at alltimes and the necessary safety and first-aid equipment must be close at hand. It is recommended thatall operations be performed in a well-ventilated fumehood in the presence and/or with the assistance ofa second worker. Most of the organophosphorus compounds used or synthesized have moderate to ex-treme sensitivity to air and their handling requires special care for this reason as well although this isnot explicitly stated in all cases.

In favor of a broad coverage of the topic within the limited number of pages available, in mostcases where full NMR spectroscopic data are available from the literature, only 1 H and 31 P NMR dataare given for a rapid identification. In this context, I wish to thank all authors for their understanding inthis point.

A representative survey of relevant literature, and, in some cases, a rather complete compilationadds to the general use of the contributions. The detailed description of the preparative procedure is the"heart" of each contribution and has been checked thoroughly for typing errors, easy understanding,reproducibility, and plausibility. When deemed necessary, drawings of the apparatus used are included.Full equations are given for all individual steps of a preparative procedure. Special care has been takenalso to address the generality of a procedure for an access to a wide range of similar compounds, thusagain enhancing the general value and use of this volume.

The material has been organized in six chapters but, due to the desired diversity on the one hand andour aim to preserve the authors' contributions in their original context on the other hand, neither astraightforward division and arrangement could be maintained nor could significant overlapping beavoided. This concept facilitates the preception and appreciation of the sequence of consecutive stepsnecessary to prepare a final product via intermediates — most of which are of interest in organophos-phorus chemistry in their own right. Hence, many of the contributions describe several quite differentcompounds of which not all belong to the class of compounds addressed in the respective chapter.Nevertheless, the arrangement in six chapters donates a certain structural body to the book which al-lows for a quick overview and will enable the reader to find related examples to a desired compoundnot explicitly described. Furthermore, all organoelement compounds mentioned in this volume arelisted in a comprehensive index and those for which detailed procedures are given are emphasized bythe use of bold face page numbers.