Compounds of Arsenic, Antimony, and Bismuth: Covering the Literature from 1937 to 1964

944 Pages·1968·79.92 MB·English

by  Michael Dub (auth.)

Volume III
COMPOUNDS OF ARSENIC, ANTIMONY, AND BISMUTH
ORGANOMETALLIC COMPOUNDS
METHODS OF SYNTHESIS
PHYSICAL CONSTANTS AND CHEMICAL REACTIONS
Volume III
COMPOUNDS OF ARSENIC, ANTIMONY, AND BISMUTH
Second Edition
Covering the Literature from 1937 to 1964
Edited by
MICHAEL DUB
Central Research Department, Monsanto Company
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
ORGANOMETALLIC COMPOUNDS
Second Edition
Voi. 1 -Compounds of Transition Metals, published m
1966
Vol. 11-Compounds of Germanium, Tin And Lead In
cluding Biologica! Activity And Commercial
Application, published in 1967
ISBN 978-3-662-01613-8 ISBN 978-3-662-01611-4 (eBook)
DOI 10.1007/978-3-662-01611-4
Ali rights reserved, especially that of translation into foreign languages
It is also forbidden to reproduce this book, either whole or in part, by photomechanical means
( photostat, microfilm and/or microcard or any other means)
without written permission from the Publishers
© 1968 Springer Science+Business Media New York
Originally published by Springer-Verlag New York lnc. in 1968
Softcover reprint of the hardcover 2nd edition 1968
Library of Congress Catalog Card Number 66-28249
Title No. 4359
PREFACE TO THE SECOND EDITION
The aim of this compilation has been to provide a comprehensive, non-criti
cal source of information concerning organometallic compounds. The scope is
limited to the compounds containing at least one carbon-metal bond. The in
formation includes methods of preparation, properties, chemical reactions,
and applications.
The First Edition comprised the literature from 1937 to 1958. The Second
Edition is completely revised and extended through 1964. The literature
prior to 1937 was thoroughly covered by E. Krause and A. von Grosse in I~ie
Chemie der meta11-organischen Verbindungen, " Verlag von Gebrueder Borntraeger,
Berlin, 1937.
Our work consists of three volumes. Volume I contains derivatives of the
transition metals of Groups III through VIII of the Periodic Table. Volume
II contains derivatives of germanium, tin, and lead. Volume III contains
derivatives of arsenic, antimony, and bismuth.
The compilation is based on searches through Chemical Abstracts. The col
lection of references for 1964 was completed before the Subject Indexes to
Volumes 60 and 61 of the Abstracts were available; thus some omissions in the
coverage of that year are possible.
We have attempted to make the coverage of the literature complete in order
that the compilation may have best utility to the chemist, chemical engineer,
patent attorney, and editor. In the interest of brevity, certain numerical
data are omitted, but references to the original literature are given. Yield
data are rounded to two significant figures. Wherever possible, tables have
been used. The entries in the Bibliography section include references to
Chemical Abstracts.
I am indebted to Dr. R. S. Gordon, Director of the Central Research
Department, and to Mr. W. A. Wilkinson, Head of the Information Center,
Monsanto Company, for their generous support of this project. I am also
indebted to Dr. R. W. Weiss, the Coeditor of Volume II, for his invaluable
advice on the form of this compilation. My thanks are due to the library
staff at the Information Center for their assistance and especially to
Mrs. Mary Alice Doiron for the preparation of the typescript for the photo
offset printing.
Michael Dub
St. Louis, Missouri
Janu"ary 1966
III
INTRODUCTION TO VOLUME III
This volume comprises organic derivatives of arsenic, antimony, and bis
muth. As in the preceding two volumes, the coverage is limited to compounds
containing at least one carbon-to-metal bond. In addition to methods of syn
thesis, physical properties, and chemical reactions, the data given in this
volume also include biological activities and uses. Pharmacological proper
ties and medicinal uses are excluded.
To facilitate the use of this volume and a correlation of analogous types
and individual derivatives of the three elements, the information on each of
the elements is divided into the following main groups:
1. Compounds of trivalent elements
2. Compounds of pentavalent elements
3. Heterocycles containing the tri- or pentavalent elements.
In groups 1 and 2 the compounds are arranged in the order of decreasing
number of organic ligands linked to the central element. Thus, in the first
main group, tertiary arsines are followed by secondary and primary arsines,
and by arsines containing arsenic linked to halogens, pseudohalogens, oxygen,
sulfur, selenium, nitrogen, phosphorus, and to metals, respectively. Com
pounds with arsenic-silicon and arsenic-boron bonds appear with the compounds
containing arsenic-to-metal bonds. The same classification is used for the
derivatives of trivalent antimony and bismuth.
In the second main group, the compounds are arranged according to the num
ber of organic ligands decreasing from five to one. Each of the subgroups
is further subdivided, depending on the heteroatoms linked to the central
element, in the same succession as that used for the compounds of the tri
valent elements.
Heterocyclic derivatives of the tri- and pentavalent elements are arranged
according to the size of the heterocycles, from four-membered to ten-membered
ring systems. Further subdivision within a ring size group is obvious from
the table of contents.
In numerous groups, compounds for which many literature data were reported
are described individually, while others, for which only a few data are
available, are compiled in tables. The individual entries as well as the
compounds in the tables are arranged in the order of increasing carbon and
hydrogen contents.
v
Coordination derivatives with arsines, stibines, and bismuthines are repre
sented by simplified molecular formulae. To distinguish covalent from ionic
ligands in the coordination compounds, the covalently bonded ligands are
enclosed with the electron acceptor within brackets or braces. However, in
some cases this classification is not certain due to lack of appropriate
data.
The nomenclature is generally in agreement with that used by the Chemical
Abstracts.
My thanks are due to my colleague Mrs. Beverly J. Edwards of the Central
Research Department for helpful discussions and criticism.
Michael Dub
St. Louis, November 1967
VI
ABBREVIA TlONS AND SYMBOLS
The following abbreviations are used in addition to, or at variance with,
those in Chemical Abstracts:
BiPy bipyridyl
(1- or 2-)C10H7- naphthyl radical
-C10He- naphthylene diradical
corr. corresponding
dec. decomposition, decomposes, decomposed, decomposing
DMF dimethylformamide
GLC gas-liquid chromatography
IR infrared
liq. liquid (adjective)
m. melting point, melts at, melted at
M a metal atom in generic formulae
matI. material(s)
obtd. obtained
Pip piperidine
prod. product(s)
psi pound per square inch pressure
Py pyridine
ref. reference(s)
r. t. room temperature
rxn. reaction( s)
sub!. sublimes at, sublimed at, sublimation
substd. substituted
THF tetrahydrofuran
TLC thin-layer chromatography
UV ultraviolet
VII
CONTENTS
PREFACE TO THE SECOND EDITION III
INTRODUCTION TO VOLUME III V
ABBREVIATIONS VII
ARSENIC
1. COMPOUNDS OF TRIVALENT ARSENIC 1
1.1 Tertiary Arsines 1
1.1.1 Symmetric Derivatives 1
1.1.2 Unsymmetric RaR'As Derivatives 33
1.1·3 Unsymmetric and Asymmetric RR'RHAs Derivatives 72
1.1.4 Ditertiary Arsines 79
1.1.5 Tritertiary Arsines 104
1.1.6 Tetratertiary Arsines 109
1.1.7 Polymers with Tertiary Arsine Groups 113
1.2 Secondary Arsines 114
Primary Arsines 119
1.4 Compounds with As-As Bonds 122
1.4.1 Diarsines 122
1.4.2 Arseno Derivatives 128
1.4.2.1 Symmetric Arseno Compounds 128
1.4.2.2 Unsymmetric Arseno Compounds 143
1.5 Compounds with Arsenic-Halogen and Arsenic-Pseudohalogen
Bonds
Secondary Haloarsines, RaAsX and RR'AsX
Primary Dihaloarsines, RAsX2
Halohydroxy- and Haloalkoxyarsines, RAs(OH)X and
RAs(OR ')X 199
Haloaminoarsines, RAs(NR'2)X 199
Secondary Pseudohaloarsines, RaAsX and RR'AsX 201
Primary Dipseudoha1oarsines, RAsX2 206
1.6 Compounds of Arsenic Bonded to Group VIA Elements 206
1.6.1 Compounds with Arsenic-Oxygen Bonds 206
IX
1.6.1.1 Arsinous Acids 206
1.6.1.2 Arsinous Acid Esters 208
1.6.1.3 Arsinous Acid Anhydrides with Carboxylic Acids 212
1.6.1.4 Oxybisarsines, (R2As)20 and (RR'As)20 212
1.6.1.5 Arsonous Acids and Monothio Analogs 219
1.6.1.6 Arsenoso Compounds 226
1.6.1.7 Arsonous Acid Esters 250
1.6.1.8 Arsonous Acid Anhydrides with Carboxylic and Phosphorus
Acids 256
1.6.1.9 Oxybis(hydroxyarsines), [RAs(OH) JeO 257
1.6.2 Compounds with Arsenic-Sulfur Bonds 258
1.6.2.2 Thioarsinous Acid Esters with Thio1s 258
1.6.2.3 Thioarsinous Acid Anhydrosulfides with Thioacids 261
1.6.2.4 Thiobisarsines, (R2As)2S and R2AsSAs(S)R2 262
1.6.2.5 Dithioarsonous Acids 263
1.6.2.6 Thioarsenoso Compounds 263
1.6.2.7 Dithioarsonous Acid Esters with Thio1s 265
1.6.2.8 Dithioarsonous Acid Anhydrosu1fides with Thioacids 278
1.6.3 Compounds with Arsenic-Selenium Bonds 285
1.6.3.2 Selenoarsinous Acid Esters with Seleno1s 285
1.7 Compounds of Arsenic Bonded to Group VA Elements 285
1.7.1 Compounds with Arsenic-Nitrogen Bonds 285
1.7.1.1 Aminoarsines, R2AsNR'2 285
1.7.1.2 Iminoarsines 288
1.7.1.3 Arsinoammonium Derivatives 288
1.7.1.4 Diarsinoamines, (R2As)2NR' 288
1.7.1.5 Triarsinoamines, (R2As)sN 288
1.7.1.6 Diaminoarsines, (R2N)2AsR' 289
1.7.2 Compounds with Arsenic-Phosphorus Bonds 290
1.8 Compounds of Arsenic Bonded to Metals 294
1.8.1 Compounds with Elements of Groups IA - IVA 294
1.8.1.1 Compounds with Alkali Metals 294
1.8.1.2 Compounds with Group IIA Metals 297
1.8.1.3 Compounds with Group IlIA Elements 297
1.8.1.4 Compounds with Group IVA Elements 298
1.8.2 Compounds with Transition Metals 299
1.8.2.6 Compounds with Group VIB Metals 299
1.8.2.7 Compounds with Group VIIB Metals 301
1.8.2.8 Compounds with Group VIIIB Metals 302
Miscellaneous Compounds
x