Newton - A Textbook of Inorganic Chemistry Vol XI Organometallic Compounds Part I
Transcript of Newton - A Textbook of Inorganic Chemistry Vol XI Organometallic Compounds Part I
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I n E L E V E N V O L U M E S . M e d i u m S vo . C l o t h . P r i c e s a r e n e t . P o s t a g e e x t r a .
A T E X T - B O O K O F
J.
V O LU ME I .
V O L U M E I I .
V O L U M E I I I .
V O LU ME I V .
V O LU ME V .
V O LU ME V I .
V O LU ME V I I .
V O L U M E V I I I .
V O L U M E I X .
V O L U M E X .
V O L U M E X I .
EDITED BY
NEWTON FRIEND, D.Sc.,
PH.D.,
F.I.C.,
Carnegie Gold Medallist.
An In t roduct ion to Modern Ino rga nic Chemis t ry . By J . N E W T O N
F R I E N D , D . S C . ( B ' h a m ) , P h . D . ( W i i r z ) ; H . F . V . L I T T L E , B . S C
(Lond.) , A.K .C.S. , Chief Ch em ist to Th oriu m , Ltd . ; W . E . S.
T U R N E R , D . S C . (Lo nd .) . Th e In er t Gases. By H . V. A. B R I S C O E ,
D.Sc. (Lond.) , A.R.C.S. Third Edition. Pp . i -xv + 38 5. 12s. 6d .
The Alkal i Metals an d their Con geners. By A. J A M I E S O N W A L K E R ,
Ph .D . (Held . ) , B .A. (Q.U.B. ) , F . I .C . Pp . i-xxvi +3 79 . 20s.
/ P A R T I . The Alka l ine E ar th M etals . By M A Y S Y B I L B U R R {nee
L E S L I E ) , D . S C .
(Leeds) . P p .
i-xxvi
+ 346. 20 s.
I P A R T II . Beryl l ium and i ts Con geners. By J O S H U A C. G R E G O R Y ,
B.Sc. (Lond.) , F . I .C. , and M A Y S Y B I L B U R R , D . S C . (Leeds) .
\ P p. i -x xv i+ 320. 183.
[Aluminium a nd i t s C ongeners , inc luding the R are E ar th M eta ls .
J By H. F . V. L I T T L E , B . S C . (Lond.) , A.R.C.S. , Chief Chemist to
{ Thor ium , L td . Second Edition. Pp . xxvi i i +485. 18s.
| Carbon an d its Allies. B y B . M. C A V E N , D.Se . (Lond. ) , F . I .C.
t Second Edition, P p .i-xxi +4 6S . 18s.
P A R T I . Nitrogen. Bv E. B . B . P R I D E A U X , M . A . , D . S c , F . I . C ,
and H . L A M B O U R N E , M.A., M.Sc ., F . I .C P p . i -xxvi i i - f 242. 18s.
P A R T I I . Phosp horus and i t s Congeners . By E . B . B . P R I D E A U X ,
M.A. , D .Sc , F . I .C , B . D . SH A W , B . S C , P h . D . , a n d W . E .
T H O RN E Y CR O FT , B . S C In Preparation.
P A R T I I I . Vanad ium , Niob ium , and Tan ta lum . By S Y D N E Y
M A R K S , M . S C , A. I .C. In Preparation.
('PART I . Oxygen. Bv J . N E W T O N F R I E N D , D . S C , a n d D O U G L A S
F . Tw iss , D .S c , F . I .C . P p . i -xx v i+3 70 . 18s .
P A R T I I . Sulphur , Se lenium, and Tel lur ium . B y B E E C E H .
VALLANOE, M . S c , D O U G L A S F . T W I S S , D . S C , an d Miss A. B .
R U S S E L L , B . S C . In Preparation.
P A R T
I I I . Chrom ium and i ts Congeners . By
B E E C E
H .
V A L L A N C E ,
M . S c , A . I . C , a n d A R T H U R A . E L D R ID G E , B . S C , F . I .C .
P p . i-x xv i+ 3S0. 18s.
("The Halo gens an d the ir Allies. B y G E O F FR E Y M A R T I N . D . S C ,
-j Ph .D . , an d E R N E S T A . D A N C A S TE R , B . S C (Lond . ) . Second
[ Edition.
P A R T I . Cobalt , Nickel , an d the Elem ents of th e Pl at in um
Group. By J . N E W T O N F R I E N D , D . S C . ( B ' h a m ) . Second Edition.
P p . i - x x v i + 367. 18s.
P A R T I I . I ro n an d i t s Com pounds . By J. N E W T O N F R I E N D ,
D.Sc. Pp.
i-xxvi
+265. 18s.
( The Metal-Ammines , wi th a Genera ] In t roduc t ion to the Theory
of Com plex Ino rga nic Sub stan ces . By Miss M. M. J . S U T H E R -
t L A N D , D .S c , F . I .C . Pp . i -xxv i+ 260 . 18s.
Organometal l ic Compounds.
P A R T I. Derivatives of th e Elem ents of Groups I to IV.
B y A R C H I B A L D E . G O D D A R D , M . S C , . A . I . C , a n d
D O R O T H Y G O D D A R D , M . S C . P p . i - x x v i i i + 4 1 8 .
P A R T II . Derivat ives of Arsen ic. B y A R C H I B A L D E . G O D D A R D ,
M . S C , A . I . C In Preparation.
P A R T
i n . Derivat ives of the Elem ents of Groups V to
VIH
(excluding Arse nic) . B y A R C H I B A L D E . G O D D A R D ,
M . S C , A . I .C . In Preparation.
LONDON; CHARLES GRIFFIN & C0.
3
LTD., 42 DRURY LANE, W.C. 2
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THE PERIODIC TABLE.*
P E R I O D S .
F i r s t s h o r t p e r i o d .
S e c o n d s h o r t p e r i o d
F i r s t ( E v a n s e r ie s .
l o n g J
i
,eriod
[odd .
S e c o n d ( E v e n s e r ie s
l o n g 4
P
e r i o d
[O d d .
T h i r d l o n g p e r i o d .
F o u r t h l o n g p e r i o d .
F i f t h
l o n g -
p e r i o d
' E y e n s e r i e s
.Od d .
V o l u m e in t h i s s e r i e s
o f t e x t - b o o k s .
G H O U P 0
1
G i t o u r I
1
2
H e
4- 0 0
10
K e
2 0 - 2
1-008
3
L i
6*940
I ;/
122 997
t8 19
A
p
K
3 9 * 9 1 3 9 - 0 9 6
29
C u
| 68*57
36
K r
82*9
5 4
X
1 3 0 - 2
86
R n
2 2 2
1
| 37
R b
{85*44
1 Ag
107-880
55
O s
1 3 2 - 8 1
66 67
D y H o
1 6 2 * 5 2163-4
79
A u
197*2
87
2
G H O U P I I
4
B e
9-02
12
M g
2 4- 3 2
20
C a
4 0 - 0 7
30
Z n
6 5 - 3 8
38
S r
8 7 - 6 3
4 8
C d
1 1 2 - 41
56
B a
137*37
6 8 69
E r T m
1 6 7 7 1 6 9 * 4
SO
H g
2 0 0 - 6 1
88
R a
2 2 5 95
3
G R O U P
I I I .
5
B
10*82
13
A l
2 6 - 9 7
21
S c
45 - 1 0
3t
G a
69*72
39
Y
88-9
4 9
I n
1 1 4 - 8
57
L a
138*90
70 71
Y b Lu
1 7 3 - 6 175-0
81
T l
2 0 4 - 3 9
89
A c
4
G i t o u r IV,
6
0
1 2 - 0 0 0
/ 4
S i
28*06
2 2
T i
48 * 1
3 2
G e
7 2 - 6 0
40
Z r
9 1 - 0
5 0
S n
1 1 8 7 0
58 59
C e P r
140*25 140-92
72
H f
[ 1 8 0 - 8 ]
8 2
P b
2 0 7 ' 2 0
90
T h
2 3 2 - 1 5
5
G n o u r V.
7
N
l i ' O O S
15
P
3 1 - 0 2 7
23
V
5 0 - 9 6
3 3
A s
74-96
4 i
N b
93*1
51
S b
121*77
60 61
N d
1 44- 2 7
73
T a
1 8 1 - 5
83
B i
209-00
91
P a
6
G H O U P Y I.
8
0
1 6 - 0 0 0
/ 6
S
3 2 - 0 6 4
24
O r
5 2 - 0 1
3 4
So
7 9 2
4 2
M o
9 6 - 0
5 2
T e
1 2 7 - 5
62 63
S m E u
1 5 0 43 152-0
G R O U P VII.
9
F
19*00
17
C I
3 5 - 4 5 7
25
M n
5 4 - 9 3
35
B r
79 916
4 3
53
I
1 2 6 - 9 3 2
6 4 65
G d T b
157-26 159'2
7 4
75
w
1 8 4 - 0
8 4
P o
[ 2 1 0 ]
9 2
U
2 3 8 - 1 7
7
85
8
G n o r p V11I.
2 6 27 28
F e Co Ni
5 5 * 8 4 58 94 5 8 - 6 9
4 4 45 46
R n Rh Pd
1 0 1 - 7 1 0 2 - 9 1 106-7
76 77 78
O s Ir P t
1 9 0 - 8 193-1 195*23
9
The International Atomic Weightsfor1925areadoptedin this Table.
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Printed in Great Britain by
NEI LL & Co. , LTD . , ED I NBURGH.
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GE NE RAL INT ROD UCT ION T O T HE SE RIE S .
D U R I N G the past few years the civiMsed world has begun to realise the
advantages accruing to sc ient i f ic research , wi th the resul t tha t an ever -
increas ing amount of t ime and thought i s be ing devoted to var ious
branches of science.
No s tu dy has progressed m ore rapid ly th an ch em is t ry . This
science may be divided roughly into several branches : namely, Organic,
Ph ys ica l , Inorg anic , and Ana lyt ica l Che m is t ry . I t i s imposs ib le to
w r i te an y s ingle tex t -b oo k wh ich sha ll conta in w i th in i t s two covers a
t h o r o u g h t r e a t m e n t o f &ny one of these branches, owing to the vast
am ou nt of i n fo rmat ion tha t has been accum ula t ed . Th e need is r a th e r
for a ser ies of text-books deal ing more or less comprehensively with
each b ra nch of chem is t ry . Th i s has a l r eady been a t t e m pte d by
enterpr is ing f i rms, so far as physical and analyt ical chemistry are
co n ce rn ed ; an d th e pres en t series is designed to m eet th e needs of
inorgan ic chem is ts . One gre a t ad va nta ge of th i s proc edu re lies in
the fact that our knowledge of the dif ferent sect ions of science does not
progress a t th e sam e ra te . Consequ ent ly , as soon as an y p ar t icular
par t advances out of propor t ion to o thers , the volume deal ing wi th
that sect ion may be easi ly revised or rewri t ten as occasion requires .
Some method of classi fying the elements for t reatment in this way
is clear ly essent ial , and we have adopted the Per iodic Classi f icat ion
wi th s l ight a l te ra t ions , devot ing a whole volume to the cons idera t ion
of the elements in each ver t ical column, as wi l l be evident f rom a glance
at the scheme in the Front i spiece .
In the f i rs t volume, in addi t ion to a detai led account of the elements
of Group 0, the general pr inciples of Inorganic Chemistry are discussed.
Par t icular pa ins have been taken in the se lec t ion of mater ia l for th i s
vo lume , and an a t t empt has been made to p resen t t o the r eader a
clear account of the pr inciples upon which our knowledge of modern
Inorganic Chemis t ry i s based.
At the outse t i t may be wel l to expla in tha t i t was not in tended
to w r i te a com ple te tex t -b oo k of Ph ys ica l Che m is try . Nu m erous
excel lent works have a l ready been devoted to th i s subjec t , and a
volume on such l ines would scarce ly serve as a su i table in t roduct ion
to th i s ser ies . Whi l s t Phys ica l Chemis t ry dea ls wi th the genera l
pr inciples appl ied to al l branches of theoret ical chemistry, our aim
has been to emphas ise the i r appl ica t ion to Inorganic Chemis t ry , wi th
which branch of the subject this ser ies of text-books is exclusively
con cerne d. To this end prac t ical ly al l th e i l lust rat io ns to th e laws
and pr inciples discussed in Volume I . deal wi th inorganic substances.
Again , there are many subjec ts , such as the methods employed in
the accura te de terminat ion of a tomic weights , which are not genera l ly
regard ed as form ing p ar t of Ph ys ic a l Che m is t ry . Y e t the se are
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vnx
ORGANOMETALLIG COMPOUNDS.
s ub j ec t s of s up r em e im po r t an ce t o t h e s t u de n t o f I no r ga n i c Ch em is t r y
and a r e acco r d ing ly i nc luded i n t he In t r oduc t i on .
H y d r o g e n a n d t h e a m m o n i u m s a l ts a r e d e a l t w i t h in V o l u m e I I . ,
a l ong w i th t h e e l emen t s of Gr o up I . T he pos i t ion of t h e r a r e ea r t h
meta l s in the Per iod ic Clas s i f i ca t ion has fo r many year s been a source
of d i ff icu lty. Th ey hav e a ll been inc lu ded in V olum e IV. , a long w i th
th e E l em en t s o f Gr o up I I I . , as t h i s was f ound t o be t h e m os t s u i t ab l e
p lace fo r them.
M an y a ll oys and com poun ds hav e an eq u a l c la im to be cons ide r ed
in two or more vo lumes o f th i s s e r i es , bu t th i s would en ta i l unnecessary
du pl ica t io n . F o r exam ple , a l loys of cop per an d t in m igh t be de a l t
w i th in Vo lum es I I . and V. r espe c t ive ly . S im i la r ly , ce r t a in do ub le
s a l ts s uch , fo r exam ple , a s f e rr ous am m on iu m s u lph a t e m igh t v e r y
log ica ll y be i nc luded i n Vo lum e I I . un de r am m on ium , an d i n V o lum e I X .
un de r i ron . As a gene ra l ru le th i s di ff icu lty h as been ov erco m e b y
t r ea t i ng complex s ubs t ances , con t a in ing two o r mor e me ta l s o r ba s es ,
i n t ha t vo lume dea l i ng w i th t he me ta l o r ba s e wh ich be longs t o t he
h ighes t g ro up of th e Per iod ic Ta b le . F o r exa m ple , th e a l loys o f cop per
and t in a re de ta i l ed in Volum e V. a long w i th t in , s ince copp er occurs
ear li e r, nam ely , in Volum e I I . S imi la r ly , f e r rous am m on iu m s u l ph a te
is d i scussed in Volum e IX . un de r i ron , and n o t un de r am m on iu m in
Volum e I I . Th e fe rro -cyan ides a re l ikewise de a l t w i th in V olum e I X .
Bu t even wi th t h i s a r r angemen t i t ha s no t a lways been f ound eas y
to a do pt a per fec t ly log ica l l ine of t r e a tm e n t . Fo r ex am ple , in t h e
c h r o m a t e s a n d p e r m a n g a n a t e s t h e c h r o m i u m a n d m a n g a n e s e f u n c ti o n
as par t o f the ac id r ad ic les and a re ana logous to su lphur and ch lor ine
in su lpha t e s and pe r ch lo r a te s ; s o t h a t t he y s hou ld be t r e a t e d i n t h e
vo lume dea l ing wi th the meta l ac t ing as base , namely , in the case
of p o t a s s iu m p e r m a n g a n a t e , u n d e r p o t a s s i u m i n V o l u m e I I . B u t t h e
a lka l i permangana tes posses s such c lose ana log ies wi th one ano ther
t h a t s epa r a t e t r e a tm en t of t he s e s a l ts ha r d ly seems des i r ab l e . Th ey
are there fore cons idered in Volume VII I .
Numerous other l i t t le i r regular i t ies of a l ike nature occur , but i t i s
hoped tha t , by means o f ca re fu l ly compi led indexes and f r equen t c ross -
re fe renc ing to the t ex t s o f the separa te vo lumes , the s tuden t wi l l
exper ience no di f f icul ty in f inding the informat ion he requires .
P a r t i cu l a r ca r e has been t aken wi th t he s ec t i ons dea l i ng w i th t he
atom ic w eigh ts of th e e lem ents in qu es t ion . T h e f igures g iv en ar e not
necessar ily tho se to be found in th e o r ig in a l m em oi r s , b u t h av e be en
reca lcu la ted , excep t wh ere o therw ise s t a ted , us ing th e fo llowing
f undamen ta l va lues :
H y d r o g e n = 1-00762. O xy gen = 16-000.
Sod ium = 22-996. Su lp h ur = 32-065.
Po tas s ium = 39-100 . F lu or ine = 19-015 .
Silver = 107-880. C hlorin e = 35-457 .
Ca rbon = 12-003. B ro m in e = 79-916.
N i t ro ge n = 14*008. Iod ine = 126-920.
By adopt ing th i s method i t i s easy to compare d i r ec t ly the r esu l t s o f
ear l i e r inves t iga to r s wi th those o f more r ecen t da te , and moreover i t
r ende r s t he da t a f o r t he d i f f e r en t e l emen t s s t r i c t l y compar ab l e t h r ough
out the whole ser ies .
Our a im has no t been t o make t he vo lumes abs o lu t e ly exhaus t i ve ,
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GENERAL INTRODUCTION TO TH E SE RIES . ix
as t h i s would r end e r t h em unn ecessa r il y bu lky and ex pe ns ive ; r a th e r
ha s i t bee n to co n t r ib u te concise and su gges t ive acc ou nts of th e var ious
topics , and to append numerous re fe rences to the l eading works and
m em oi rs dea l ing w i th th e sam e. E v ery e ffort ha s bee n m ad e to render
these references accurate and re l iable , and i t i s hoped that they wi l l
pro ve a useful fea tu re of th e se r ies . T h e m ore im p o r ta n t abb revia t ions ,
which a re subs t an t i a l l y t he same a s t hose adop t ed by t he Chemica l
Socie ty, are deta i led in the subjoined l i s t s , pp. xvi i -xix.
The addi t ion of the Table of Dates of Issue of Journals (pp . xx i -xx vi i i )
wi l l, i t is hoped , en ha nc e th e valu e of th is ser ies . I t is bel ieved th a t
the l ist is perfect ly correct , as al l the f igures have been checked against
the volumes on the shelves of the l ibrary of the Chemical Socie ty by
Mr. F. W. Clifford and his staff. To t hese gen t l em en th e E d i to r and
the Authors des i re to express the i r deep indebtedness .
In order tha t the se r i es sha l l a t t a in the maximum ut i l i ty , i t i s
necessa ry t o a r r ange fo r a ce r t a in amount o f un i fo rmi ty t h roughout ,
and th i s involves the suppress ion of the persona l i ty of the indiv idua l
author to a cor responding extent for the sake of the common wel fa re .
I t is a t once m y d u ty an d m y pleasure to express m y s incere a pp re
c i a ti on of t he k ind and r ea dy man ne r i n which t he au tho r s hav e
accommodated themselves to th i s t ask , which , wi thout the i r hear t}?-
co-o perat ion , could nev er h av e been successful . F in al ly, I wish to
acknowledge the unfa i l ing cour tesy of the publ i shers , Messrs . Char les
Griffin & Co., w ho h av e do ne ev ery thin g in th ei r po w er to ren de r th e
work s t ra ight forward and easy .
J . N E W T O N F R I E N D .
September1928.
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P R E F A C E .
T H E present book a ims a t g iv ing a to lerab ly complete account of the
pre pa rat io n and prope r t ies of th e organic co m poun ds of th e e lements of
Grou ps I . to IV . of th e Pe riod ic Classificat ion. E xc ep t in th e case of
m ercu ry , no mon ogra ph has ap pea red in an y languag e which deals wi th
the organic compounds der ived f rom the e lements of these groups .
T h e t e r m organometallic as used in this volume is appl ied only to com
po un ds co ntaining a second e lem ent direct ly l inked to carbo n, an d
excludes those where the element is l inked viao xyg en or nitro ge n, as well
as double com pound s of organic substance s w i th inorganic sa l t s . In
spi te of these omissions, the present volume gives an account of approxi
m ate ly 2300 com poun ds. In order to m ak e th e book as com plete as
poss ib le , the preparat ion of a l l key compounds has been given in detai l ,
an d i t m ay be used as a t re at i se on prac t ical o rganic che m is t ry . S ince
i t has been necessary to cover so much ground no sys temat ic a t tempt
has been made to en ter in to theoret ical aspects of the subject , bu t by
endeavouring to include al l known compounds chemists wil l be able to
make valuable compar isons of the compounds of the var ious e lements ,
which was h i ther to impossib le wi thout consul t ing a vas t amount of
or ig inal l i tera ture . To m ak e th e te x t m ore readab le , physical con stan ts
of large ser ies of compounds have been placed in the Appendix, and
th roughou t the book g rea te r a t t en t ion has been pa id to phys ica l p ro
per t ies generally th a n i s us ua l in th is typ e of boo k. Th e A utho rs '
exper ience has shown that such data would have been very usefu l in
their own research work i f i t had been avai lable in book form.
In conclus ion , the Authors wish to thank the Edi tor , Dr . J . Newton
Fr iend , for h is invaluable help in reading the whole of the manuscr ip t
an d proofs , to M essrs. F la ck an d S m ith of th e Lib rary of th e U nive rs i ty
of B irm ing ha m , for giving t h e A ut ho rs free access to an y port ion of
th e L ib r a ry , and to E . M as te r s . B .S c , A.R.C.S . , fo r l end ing th e A uthors
his copies of the Journal of th e A m erican Chem ical Society . R ep rin ts
of or iginal papers deal ing with organometal l ic compounds wil l be
thankfu l ly received by the Authors .
A . E . G O D D A R D .
D . G O D D A R D .
September1928.
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xiv
ORGANOMETALLIC COMPOUNDS.
P A G E
C H A P T E R VII. M e r c u r y (continued) . . . . 1 1 0
DERIVATIVES OFAEOMATIOAM INESG eneralAnilineH alogenatcdAnilines
NitroanilinesMono-andDi-AlkylanilinesBenzylanilineAcid Anilides
Diphenylaminea-Anilido-Fattv Acids and their EstersTolylglycine
EstersToluidines andToluididesBenzidineNaphthylamines and their
Sulphonic Acids.
CHAPT E R V I I I . M e r c u r y (continued) . . 1 3 6
DERIVATIVES OF AROMATIC COMPOUNDS CONTAINING HYD ROX YL GR OU PS
GeneralPhenolAnisole Phenetole NitrophenolsAminophenol
CresolsThymol CaivacrolAlkyl PhenolsGuaiacolSafrol
Eugenol Methyl Ether Resorcinol Naphthols and their Sulphonic
AcidsSalicyly} Alcohol (Saligenin)p-Hydroxy-m-Xitrophenyl Carbinol.
CHAPT E R IX. M e r c u r y (continued) . . . . 160
DERIVATIVES OF AROMATIC ACIDSGeneralBenzoic Acid and its Esters
Thiolbenzoic AcidNitrobenzoic A oidsSalicylic Acid
and its
Esters
Nitrosalicylic AcidAnthranilic EstersSubstituted Anthranilic Esters
wa-Arninobenzoic Acid^-Aminobenzoic Acid and its EstersCinnamic
Acidand itsEsters"/?-Hydroxynaphthoic Acid.
CHAPT E R X. M e r c u r y (continued) . . . . 180
MISCELLANEOUS MERCURY DERIVATIVESO FORGANICCOMPOUNDSDerivatives of
OlefmesCompounds from AcetyleneandPhenylacetyleneDerivativesof
Cyclo-andDicyclo-PentadieneAlkyl and Aryl Mercuric Alkyl Xanthates
DerivativesofSubstituted Aryloxy-Fatty AcidsDerivativesofHydrazines
Derivative
of
PyrimidmeDerivatives
of
Salicyl
and
Mtrosalicyl Alde
hydesDerivatives of m-and ji-Hydroxy-benzaldehydes and their Nitro
compoundsDerivativesofAcetophenoneDerivativesofBenzophenone
Derivatives of Indandione and OxindoneDerivatives of Camphor, Cam
phor-Carboxy lie Acid, CampheneDerivativesofTerpineol and Dimethyl-
heptenol, Allyl Acetoxime, Methylheptenone Oxime, Ethylhexenol
Derivatives of Azo CompoundsDerivatives of Hydroxyazobenzenes
Derivatives of Methylene BlueDerivatives of PhthaleinsCyclomercuri-
polyniethylenes Derivatives of the Pyrazolone GroupDerivatives of
PyridineDerivatives of Furane andPyrroleDerivatives of the Indole
SeriesDerivatives
of
QuinolineDerivatives
of
Dihydrobenzofuranes
Derivatives containing MercuryandSelenium.
CHAPT E R XI. O r g a n o m e t a l l i c D e r i v a t iv e s of the M e t a l s
o f G r o u p I I I . . . . . . . 219
GeneralBoron: AIMCompounds of the Types R
3
B,R.B.OH, RB(OH)
2
Aryl Compoundsof theTypesR
3
B ,R
2
BX, RBX
2
, R
2
B.OH, RB(0H)
2
,RBO.
Aluminium : Alkyl Compoundsof theTypes R
3
A1, R
2
A1X, RA1X
2
Aluminium
Trialkyl EtheratesCompounds from Methylene IodideArvl Compounds
of
the
Type R
3
A1.
Indium: Indium Diphenyl Chloride, Indium Phenyl Oxide.
Thallium; Alkyl Derivativesof theType R
2
T1X, Aryl Derivativesof theType
R
2
T1X.
CHAPTER XII . O r g a n o m e t a l l i c D e r i v a t i v e s of the M e t a l s
o f G r o u p IV. . . . .
#
246
GeneralSilicon: Alkyl Derivativesofthe Types R
4
Si,R
s
SiR',RaSiR^R.SiR'R",
R
3
SiX, R
2
SiX
2
, RSiX
3J
R
3
Si(OH), R
3
Si(0R), R
2
Si(OR)
2
, R.,Si(0R)Hal.,
RSi(OR)
3
, Si(0R)
8
HaL, (R
3
Si)
2
0, R
2
SiO, R.SiO.OH, R
3
Si.SiR:Aromatic
Derivativesof theTypes R
4
Si, R
3
SiX, R
a
SiX
s
, RSiX
3
, R
3
Si(0H}, RSi(OH)
9
,
(RSiO)
2
0, R
2
SiO, 5 KOR^), XSi{OR^)(OR^{OR), X-gi)R>)(OR),R
3
Si.SiR
35
RiR^Si .Si
KWR
3
, Si
4
Ph
8)
[SiPh
2
]
K
Silicon Compounds containing Lead, Tin, and
Arsenic.
Gerrnamum : Alkyl Derivatives of Type R
4
Ge, Aryl Compounds of the Type
B
&
Geandtheir Derivatives, Aryl Germanic Acid Anhydrides.
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CONTENTS.
xv
PAGE
C H A P T E R XI I I . Grgano metal l i c Der iv ativ es of Ti n . 300
GeneralAlkyl Derivatives of the Types R
4
Sn, R
3
SnR', R
2
SnR
2
', R^SnR'R",
R
3
SnX, R
2
R'SnX, RR'SnX
2
, RT/R^SnX, R
2
SnX
2
, R.SnO.OH," RSnX
s
,
R,Sn, R
3
Sn, R
3
Sn.SnR
a
Aryl Derivatives of the Types R
4
Sn, Ar
3
SnAr',
Ar,SnAlk, A]kAlk'SnAr
2
, AlkAlk
2
'SnAr, Alk
a
SnArJ Alk
3
SnAr, R
3
SnX,
R
2
SnX
2
, R
2
SnXX', AlkArSnX,, R
2
Sn, Ar
3
Sn.SnAr.
3
, Ar
3
Sn.SnA]k
3
,
R
3
Sn, R
2
Sn
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*
LIST OF CH IEF ABBR EVIATIONS EM PLO YED
I N T H E R E F E R E N C E S .
A B B R E V I A T E D T I T L E .
Afhandl. Pys. Kern.
Am er. Ch em. J. .
Amer. J. Sci.
Anal. Fis. Quim.
Analyst
Annalen
Ann. Chim.
Ann. Chim. anal.
Ann. Chim. Phys.
Ann. Mines
Ann. Pharm.
Ann. Phys. Chem.
Ann. Physik
Ann. Physik, Beibl.
Ann. Sci. Univ. Jassy
Arbe iten Kaiserl. Gesun dheits-
amte .
Arch. exp. Pathol. Pharma k.
Arch. Pharm.
Arch. Sci. phys. nat,
Atti Ace. Torino .
Atii JR .Accad. Lined
B.A. Reports
Ber. .
Ber. Akad. Ber. .
Ber. Deu t. physikal. Ges.
Bull. Sci. Pharma col.
Bot. Zeit. .
Bui. So c. Stiinte Glaj.
Bull. Acad. roy. Belg.
Bull. Acad. Sci. Cracow
Bull, de Belg.
Ber. Deut. pharm. Ges.
Bull. Soc. chim. .
Ball. So c. franc. M in. .
Bull. Soc. min. de Prance
Bull. U.S. Geol. Survey
Centr. Min.
Chem. Ind,
Chem. News
Chem. Weekblad .
Chem. Zeit.
Chem. Zentr.
CompL rend.
CrelVs AnnaU n .
Dingl. poly. J. .
J O U R N A L .
Afhandl inga t i Fys ik , Kemi och Minera log i .
A m er i can C h em i ca l Jo u r n a l .
Amer ican Journa l o f Sc ience .
Anales de l a Soc iedad Espaf io la F i s i ca y Quimica .
Th e A n a l y s t .
Ju s t u s L i eb i g ' s A n n a l en d e r C h em i e .
A n n a l e s d e C h i m i e ( 1 7 1 9 - 1 8 1 5 , an d 1 9 1 4+ ) .
A n n a l e s d e C h i m i e an a l y t i q u e ap p l i q u ee a F l n d u s t r i e , a
1'Agriculture, a la Pharmacie. , et a la Biologic.
Anna les de Chimie e t de Phys ique (Par i s ) (1816-1913) .
Anna les des Mines .
A n n a l en d e r Ph a r m ac i e ( 1 8 3 2 - 1 8 3 9 ) .
Anna len der Phys ik und Chemie (1819-1899) .
A n n a l en d e r Ph y s i k ( 1 7 9 9 - 1 8 1 8 , an d 1 9 G 0 + ) .
A n n a l en d e r Ph y s i k , B e i b l a t t e s .
An na les sc ient if iques de I 'TJmversi te de Jas sy .
A r b e i t en au s d em K a i se r l i c l i en G esu n d h e i t s am t e .
Arc h iv f iir expe r imen te l l e Pa tho log ic un d Pha rma kolo g ie .
A r ch i v d e r Ph a r m az i e .
Arch ives des Sc iences phys ique e t na tu re l l es , Geneve .
At t i de l l a Rea le Accademia de l l e Sc ienze d i Tor ino .
At t i de l l a Hea le Accademia L ince i .
B r i t i sh A sso c i a t i o n R ep o r t s .
Ber ich te der Deu t schen chemischen Gese l l schaf t .
See Sitzungsber. K. Akad. Wiss. Berlin.
Be r ich te de r De u t sc hen phys ika l i sch en Gese l lschaft .
B u l l e t i n d e s Sc i en ces Ph a r m aco l o g i q u es .
B o t an i sch e Ze i t u n g .
Bule t inu l Soc ie ta te i de S t i in te d in Cluj.
Academie roya le de Be lg iqueBul le t in de l a Classe des
Sciences.
Bul l e t in in te rna t iona l de l 'Academie des Sc iences de
Cracovie .
Bul l e t in de l a Soc ie te ch imique Belg ique .
B e r i ch t e d e r Deu t sch en p h a r m azeu t i s ch en G ese l l s ch a f t .
Bu l l e t in de l a Soc ie te ch imique de France .
Bul le t in de la Societe f ranchise de Mineralogie .
Bul l e t in de l a Soc ie te minera log ique de Prance .
Bul l e t ins o f the Uni ted S ta tes Geo log ica l Survey .
Cen t ra lb la t t fu r Minera log ie .
D i e C h em i sch e I n d u s t r i e .
C h em i ca l N ews .
C h em i sch Week b l ad .
Chemiker Ze i tung (Cothen) .
C h em i sch es Zen t r a l b l a t t .
C o m p t e s r e n d u s h e b d o m a d a n e s d e s S e a n c e s d e 1'Academie
des Sciences (Par is) .
C h em i sch e A n n a l en f u r d i e F r eu n d e d e r N a t u r l eh r e , v o n
D . O e l l e .
D i n g i e r ' s p o l y t ech n i sch es J o u r n a l ,
s v i i
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XV111
O R G A J S O M E T A L L I C C O M P O U N D S .
A B B R E V I A T E D T I T L E .
Drudds Annalen
Ehctroch. Met. Ind.
Eng. and M in. J.
Gazzetta . . . .
Ue hlerfs Allg. J. Chem.
Geol. Mag.
Gilbert's Annalen
Giorn. di Scicnze Natarali ed
Econ
Helv. Chim. Act'i
Int. Z&iUch. Meiallographie .
Jahrb, kk.geol.Reichsanst. .
Juhrb. Miner.
Jahresber. .
Jetiaische Zeitsch.
J. Amer. Cham . Soc.
J. Chem . Soc,
J. Ohim. phys. .
J. Gasbeleuchitiivj
J. Geology .
J. Ind. Eng. Chem.
J. I ml. M etals .
J. Miner. Soc.
J. Pharm. Chim.
J. Physical Chem.
J. Physique
J. prahi. Ghem. .
J. Russ. Phys. Chem . Soc. .
J. Soc. Ckem. Ind.
Landw . Jahrb, .
Mem. Paris Acad.
Mem. Coll.Sci. Kyo to.
Moiiaish. . . . .
Mon>. sew it.
Munch. Med, Wochenxchr, .
Nature . . . .
Ntiovo G ini,
Oesterr. Chem. Ztit
Ofvers. K. Vet.-Alcad. Forh. .
PAuger's Archil' .
Pharm. Post
Pharm. ZcMr.-k..
Phil. Mag
Phil Trans.
Phys. Review
Physical. Zeitsch.
Pogg. Annalen .
Proc. Ch em. Soc.
Proc. K. A had. Wd emch.
Amsterdam .
Proc. Roy. Irish Acad.,
Proc. Roy. Phil Soc. Glasgow
Proc. Roy. Soc. .
Proc. Roy. Soc. Edin. .
J O U R N A L .
Annalen der Physik (1900-1906).
Electrochemical and Metallurgical Industry.
Engineering and Mining Journal.
Gazzetta ohimica italiana.
Allgemeines Journal der Chemie.
Geological Magazine.
Annalen der Physik (1799-1824).
Giornale di Science Naturali ed Economiche.
Helvetica Chim. Acta.
Internationale Zeitschrift fur Metallographio.
Jahrbnch der kaiserlich-komglichen geologischcn Reichsan-
stalt.
Jahrbuch fur Mineralogie.
Jahresbericht liber die Eortschritte der Chemie.
Jenaisc he Zeitschrift f iir Naturw issenschaft.
Journal of the American Chemical Society.
Journal of the Chemical Society.
Journal de Chimie physique.
Jou rnal fur Gasbeleuchtung.
Journal of Geology.
Journal of Industrial and Engineering Chemistry.
Journal of the Institute of Metals.
Mineralogical Magazine and Journal of the Mineralogical
Society.
Journal de Pharmacie et de Chimie.
Journal of Physical Chemistry.
Journal de Physique.
Journal fur praktische Chemie.
Journal of the Physical and Chemical Society of Russia
(Petrograd). ,
Journal of the Society of Chemical Industry.
Landwirtschaitliche Jahrbiicher.
Memoirs presentes par divers savants a l'Academie des
Sciences de l ' lnstitut de France.
Memoirs of the College o^ Science, Kyoto Imperial
University.
Monatshefte tur Chemie und verwandte Theile anderer
Wissenschaften,
Moniteur scientifique.
Miinchener Medizinische Wochenschrift.
Nature.
II nuovo Cimento.
Oesterreichische Chemiker-Zeitung.
Ofveraigt af Kongliga Vetenskaps-Akademiens Edrhand-
lingar.
Archiv fur die gesammte Physiologic des Menschen und
der Thiere.
Pharmazeutische Post.
Pharinazeutische Zentralhalle.
Philosophical Magazine (The Loudon, Edinburgh, and
Dublin).
Philosophical Tran sactio ns of the R oy al Society of
London.
Physical Review.
Physikalische Zeitschrift.
Poggendorffs Annalen der Plrysik und Chemie (1824-
1877).
Proceedings of the Chemical Society.
Koninklijke Akademie van Wetenschappen te Amsterdam
Proceedings (English Version).
Proceedings of the Royal Irish Academy.
Proceedings of th e R oy al Philosop hical Society of G lasgow,
Proceedings of the Royal Society of London.
Proceedings of the Royal Society of Edinburgh.
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T A B L E O F D A T E S O F I S S U E O F J O U R N A L S .
F O R th e s ake of easy reference, a l ist is ap pe nd ed of th e mo re
im p o rta n t jou rnals in chronological order, giving th e da tes of issue of
the ir corresp ond ing series an d vo lum es. In certain eases th e volumes
have appeared wi th cons iderable i r regular i ty ; in o thers i t has occa
s ional ly happened tha t volumes begun in . one calend ar yea r hav e
ex tend ed in to th e n ex t year , even w hen th is h as n o t bee n th e genera l
ha b it of th e series . To com plicate m at te rs s ti ll further, th e t i tle-pages
in some of these la t ter volumes bear the la ter datea most i l logical
pro ced ure . In such cases th e volum e nu m be r appears in the accom
pa ny ing columns oppo s i te bo th years . In a shor t sum m ary of th is k ind
it is impossible to give full details in each case, but the foregoing
remarks wi l l serve to expla in severa l apparent anomal ies .
V p f l T
j , OCVA. *
1800
1
2
3
4
1805
6
7
8
9
1810
11
12
13
14
1815
16
17
18
19
1820
21
22
23
24
1825
26
27
28
29
i
Amer.
J. Sci.
. . .
. . .
...
..,
. . .
. . .
...
...
.
...
.
. . .
. . .
1 ,2
3-5
6-8
9-11
12-14
15-17
I
First series known as Bulletin dePharmacies
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Year.
11830
31
32
33
34
|1835
36
37
38
39
|184 0
41
4 2
4 3
44
|184 5
46
47
48
4 9
11850
51
52
53
54
|1855
56
57
53
59
Aiuer .
J .
Sci .
17, 18
19, 20
2 1 , 2 2
23, 24
25-27
2 8 , 29
3 0 , 3 1
32 , 33
34, 35
36 , 37
38, 39
40, 41
42 , 4 3
44 , 45
46, 47
48-50
( 2 ) 1 , 2
3 , 4
5, 6
7 , 8
9, 10
11 , 12
13 , 14
15, 16
17 , 18
19 , 20
2 1 , 22
23 , 24
25 , 26
27 , 28
Auuule n .
1-4
5-8
9 -12
13-10
17-20
21-24
2 5 - 2 8
2 9 - 3 2
' 3 3 - 3 6
37-40
4 1-4 4
4 5 - 4 8
4 9 - 5 2
53-56
57-60
61-64
6 5 - 6 8
6 9 - 7 2
7 3 - 7 6
7 7 - 8 0
81-84
8 5 - 8 8
8 9 - 9 2
93-96
9 7 - 1 0 0
101-104
1 0 5 - 1 0 8
1 0 9 - 1 1 2
A n n .
Ohim.
Phys .
4 3 - 4 5
4 6 - 4 8
4 9-51
52-55
56-57
58-60
61-63
64-66
w-m
70-72
73-75
(3) 1-3
4 - 6
7 - 9
10-12
13-15
16-18
19-21
22-24
25-27
2 8 - 3 0
3 1 - 3 3
3 4 - 3 6
3 7 - 3 9
4 0 - 4 2
4 3 - 4 5
46-48
4 9-51
5 2 - 5 4
55-57
i
>
j An n . ; Arc h .
i Miiiets.;P h a r m .
7-8 31 -34
i
1 ( 3 ) 1 , 2
i 3 , 4
5 , 6
I 7 , 8
: 9 , i o
i 11, 12
3 5 - 3 9
4 0 - 4 3
44-47
4 8 - 5 0
(2) 1-4
5 - 8
9-12
j 13 ,14 13 -16
15, 16
17, 18
1
19, 20
' ( 4 ) 1 , 2
3 , 4
5, 6
7 , 8
9 , 1 0
1 1 , 1 2
13 , 14
1 5 , 16
17,18
19 , 20
(5) 1, 2
3 , 4
5, 6
7 , 8
9 , 1 0
11 , 12.
13 , 14
15, 16
17-20
2 1 - 2 4
2 5 - 2 8
2 9 - 3 2
33-36
3 7 - 4 0
4 1 - 4 4
45-48
4 9 - 5 2
5 3 - 5 6
5 7 - 6 0
6 1 - 6 4
6 5 - 6 8
6 9 - 7 2
7 3 - 7 6
7 7 - 8 0
8 1 - 8 4
85-88
8 9 - 9 2
9 3 - 9 6
9 7 - 1 0 0
Bull .
Soc.
chiiu.
. . .
Conip t .
r e nd .
. . .
1
2, 3
4, 5
6. 7
... j &', 9
. . .
. . .
. . .
l
io, n
12, 13
14 , 15
16 , 17
1 8 , 19
2 0 , 2 1
22 , 23
24, 25
26 , 27
2 8 , 29
30, 31
32 , 33
34, 35
36, 37
38 , 39
40 , 4 1
42, 43
44, 45
46 , 47
48 , 49
Ding l .
poly" J .
3 5 - 3 8
3 9 - 4 2
43-47
48-50
51-54
55-58
59-62
6 3 - 6 6
6 7 - 7 0
7 1 - 7 4
7 5 - 7 8
7 9 - 8 2
8 3 - 8 6
8 7 - 9 0
91-94
9 5 - 9 8
9 9 - 1 0 2
103-106
107-110
1 1 1 - 1 1 4
1 1 5 - 1 1 8 '
1 1 9 - 1 2 2
123 126
127-130
131-134
1 3 5 - 1 3 8
1 3 9 - 1 4 2
1 4 3 - 1 4 6
1 4 7 - 1 5 0
1 5 1 - 1 5 4
J . j J".
P h a r m . p r a k t .
C h i m . Uhcin.
16
17
18
19
20
21
22
23
24
25
1-3
4 -6
7-9
10-12
13-15
16-18
26
2 7
( 3 ) 1 , 2
3 , 4
5 , 6
7 , 8
9, 10
11 , 12
13 , 14
15 , 16
17,. 18
19, 20
2 1 , 22
23 , 24
25, 26
27, 28
29, 30
3 1 , 32
33 , 34
35 , 36
1 9 - 2 1
2 2 - 2 4
25-27
2 8 - 3 0
3 1 - 3 3
34-36
3 7 - 3 9
4 0 - 4 2
4 3 - 4 5
4 6 - 4 8
4 9 - 5 1
52-54
5 5 - 5 7
5 8 - 6 0
6 1 - 6 3
6 4 - 6 6
6 7 - 6 9
7 0 - 7 2
7 3 - 7 5
7 6 - 7 8
Mon.*
s c i o n .i
P h i l
(1)1
2
3
7,8
9 10
11 (3)1
2,3
4,5
6,7
8,9
10,11
12,13
14,15
Phil.
p
gg-
Trans.Annalen.
16,
18 ,
2 0 ,
22 ,
2 4 ,
1 7
JQ
2 1
2 3
2 5
1 3 0
1 3 1
1 3 2
1 3 3
1 3 4
26,27
28,29
30,31
32,33
34,35
36, 37
(4)1,2
3, 4
5, 6
7,8
9 10
11,12
13,14
15,16
17,18
120
121
122
123
124
125
126
127
128
129
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
Proc.
R oy .
Soc.
18 -20
21-23
24-26
27-30
31-33
3 4 - 3 6
37-39
40-42
4 3 - 4 5
46-48
4 9-51
52-54
55-57
58-60
61-63
64-66
67-69
7 0 - 7 2
7 3 - 7 5
7 6 - 7 8
79-81
82-84
85-87
88-90
91-93
9 4 - 9 6
97-99
100-102
103-105
106-108
1
2
6 ,7
7
8
9
9
9, 10
1
1 , 2
2, 3
4
5
6
7
9
10
11
12
S i tz ungsbe r .
K . A k a d .
Wiss .W i e n .
1
2 , 3
4 , 5
6 , 7
8, 9
10 , 11
1 2 - 1 4
15-18
1 9 - 2 2
2 3 - 2 7
2 8 - 3 3
3 4 - 3 8
O
o
>
t-
r*
C
c
o
g
rr
o
Often referred t o b y S e r i e s : Ser ies 3 , vols. 1-16, 1 8 7 1 - 1 8 8 6 ; S e r ie s 4 , vols. 1-24 , 1 8 8 7 - 1 9 1 0 ; Ser ies 5 , vols. 1-9,1911-1919 (one vol. yearly)."
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Year.
1860
61
62
63
64
1865
66
67
68
69
1870
71
72
73
74
1875
76
77
78
79
1880
81
82
83
84
1885
86
87
88
89
Compt
rend.
50 , 5 1
52 , 53
54 , 55
66 , 57
58 , 59
6 0 , 6 1
62 , 63
64 , 65
66 , 67
68, 69
70 , 7 1
72 , 73
74,75
76 , 77
78 , 79
8 0 , 8 1
82 , 83
84 , 85
86 , 87
88, 89
90 , 91
92 , 93
94 , 95
96, 97
98, 99
100, 101
102, 103
104, 105
106 , 107
108, 109
Dingl .
poly . J .
155-158
159-162
163-166
167-170
171-174
175-178
179-182
183-186
187-190
191-194
195-198
199-202
203-206
207-210
211-214
215-218
219-222
223-226
227-2S0
231-234
235-238
239-242
243-246
247-250 -
251-254
255-258
259-262
263-266
267-270
271-274
Gazzet ta.
i
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
J . Amer.
Gliem.
Soc,
...
...
\ .
.
...
1
2
3
4
5
6
7
8
9
10
1 1
J . Chem,
Soc.
is
16
17
18
19
20
2 1
22
23
24
25
26
27
28
29 , 30
31 , 32
33, 34
35, 36
37 , 38
39 , 40
41 , 42
43, 44
45 , 46
47, 48
49 , 50
51 , 52
53,54
55, 56
J , P h a r m .
Ghini.
37 , 38
39 , 40
4 1, 42
43, 44
45, 46
(4) 1, 2
3,
4
5, 6
7 , 8
9, 10
11 , 12
13, 14
15, 16
17 , 18
19 , 20
21, 22
23 , 24
2 5, 26
27 , 28
29 , 30
(5) 1, 2
3 , 4
5, 6
7 , 8
9, 10
11,
12
13, 14
15 , 16
17, 18
1 9 , 2 0
J . prakt,
Chem.
79-81
82-84
85-87
88-90
91-93
94-96
97-99
100-102
103-105
106-108
(2) 1, 2
3 , 4
5, 6
7 , 8
9, 10
11 , 12
13, 14
15, 16
17 , 18
19 , 20
21 , 22
23, 24
2 5 , 26
27, 28
29 , 30
31 ,
32
3 3 , 34
35, 36
37,38
39,40
J , l i uss .
Pl iys.
Ghem.
Soc.
. . .
i
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
J. Soc.
Ghem.
Ind .
*-
...
* > >
. . .
.
...
...
1
2
3
4
5
6
7
8
9
10
Mon.
scient.*
4
...
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
2 2
23
24
25
26
27
28
29 , 30
31 , 32
33,34
Nature .
...
...
. . .
...
. . .
. . .
1
1 , 2 , 3
3 , 4 , 5
5 , 6 , 7
7, 8 , 9
9, 10, 11
11, 12, 13
13 , 14, 15
15, 16, 17
17 , 18, 19
19 , 20, 21
21 . 22, 23
23, 24, 25
25, 26, 27
27 , 28 , 29
29 , 30, 31
31 ,
32, 33
33, 34, 35
3 5, 36, 37
37 , 38, 39
39, 40, 41
Phi l . Mag.
19 , 20
21 , 22
23, 24
25, 26
27 , 28
29 , 30
31 , 32
33, 34
35, 36
37 , 38
39 , 40
4 1 , 42
43, 44
45, 46
4 7 , 48
49, 50
(5) 1, 2
3 , 4
5, 6
7, S
9, 10
11 , 12
13 , 14
15, 16
17 , 18
1 9 , 2 0
2 1 , 2 2
23, 24
25 , 26
27 , 28
See footnote, p . xxii.
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Year.
Phil.
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8/11/2019 Newton - A Textbook of Inorganic Chemistry Vol XI Organometallic Compounds Part I
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Ame>\
Chm,
J .
12
13
14
15
16
17
I S
19
20
21 ,
22
23 , 24
25 , 26
27 , 28
29 , 30
3 1 , 3 2
33 , 34
35 , 36
37, 38
39 , 40
41 , 4 2
43 , 44
45 , 46
47, 48 '
49, 50
Publica
tion
ceased
Amer.
J . S e t
39 . 40
41 , 42
43 , 44
45 , 46
47 , 48
49, 50
(4) 1, 2
3 , 4
5, 6
7 , 8
9, 10
11 , 12
13 , 14
15 , 16
17, 18
19 , 20
21 , 22
23, 24
25 , 26
27, 28
29, 30
31 , 32
3 3 , 34
35, 36
37, 38
3 9 , 40
41, 42
43 , 44
4 5 , 46
47, 48
Analyst.
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
'37
38
39
40
41
42
43
44
Anna len .
256-260
261-266
267-271
272-277
278-283
284-288
289-293
294-298
299-303
304-309
310-313
314-319
320-325
326-329
330-337
338-343
344-350
351-357
358-363
334-371
372-377
378-385
386-394
395-401
A n n .
C h in i .
Phys.
1 9 - 2 1
22-24
25-27
28-30
(7 ) 1 -3
4 - 6
7-9
1 0 - 1 2
1 3 - 1 5
1 6 - 1 8
1 9 - 2 1
22-24
25-27
28-30
(8) 1-3
4 - 6
7-9
1 0 - 1 2
1 3 - 1 5
1 6 - 1 8
1 9 - 2 1
22-24
25-27
28-30
. . .
. . ,
A n n .
JVlines,
1 7 , 1 8
1 9 , 2 0
( 9 ) 1 , 2
3 , 4
5, 6
7 , 8
9, 10
1 1 , 1 2
13 , 14
1 5 ,
1 6
1 7, 18
1 9 , 2 0
(10)1 ,2
3 , 4
5 , 6
7 , 8
9, 10
1 1 , 1 2
1 3 , 14
1 5 , 16
1 7 , 1 8
1 9 , 2 0
(1 1 )1 , 2
3 , 4
5 , 6
. . .
A r c h .
P h a r m ,
228
229
230
2 3 1
2 3 2
233
234
2 3 5
236
2 3 7
2 3 8
239
2 40
2 41
2 42
2 43
244
2 45
246
2 47
248
249
2 5 0
2 5 1
2 5 2
2 5 3
254
2 5 5
, . .
. . .
Bor.
2 3
24
2 5
2 6
27
28
29
3 0
3 1
3 2
3 3
3 4
3 5
3 6
37
3 8
3 9
4 0
4 1
4 2
4 3
44
4 5
4 6
4 7
4 8
49
5 0
5 1
5 2
Bull.
Soc.
i him.
3 , 4
5, 6
7 , 8
9, 10
11 , 12
13 , 14
15 , 16
17 , 18
19 , 20
2 1 ,
22
23 , 24
25 , 26
27 , 28
29 , 30
31 , 32
33 , 34
35, 36
(4)1 ,2
3, 4
5, 6
7 , 8
9, 30
1 1 , 12
13, 14
15 , 16
17, 18
19 , 20
2 1 , 22
23 , 24
25, 26
Ohom.
News .
61 , 62
63 , 64
65, 66
67, 68
69 , 70
71 , 72
73 , 74
75, 76
77,78
7 9 , 80
81, 82
83, 84
85 , 86
87 , 88
89 , 90
91 , 92
93 , 94
95, 96
97, 98
99 , 100
101,102
103,104
105,106
107,108
109,110
111,112
113,114
115,116
117
118,119
Chem.
Trade
J.
Chem.
Weelc-
blad.
6 7
8, 9
10,11
12,13
14,15
16,17
18,19
20,21
22,23
1
24,
25
26,27
28,29
30,31
32,33
34,35
36,37
38,39
40,41
42,43
44,45
46,47
48,49
50,51
52,53
54,55
56,57
58,59
60,61
62,63
64,65
4
5
6
9
10
11
12
13
14
15
16
Chem.
Zeifc.
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
Compt.
rend.
110,111
112,113
114,115
116,117
118,119
120,121
122,123
124,125
126,127
128,129
130,131
132,133
134 135
136,137
138,139
140,141
142,143
144,145
146,147
148,149
150,151
152,153
154,155
156,157
158,159
160,161
162,163
164,165
166,167
168,169
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Year ,
1890
91
92
93
94
1895
96
97
98
99
1900
01
02
03
04
1906
06
07
08
09
1910
11
12
13
14
1915
16
17
18
19
Ph i ) .
T r a n s .
i . 181
182
183
184
185
186
387, 188
189, 190
191
192, 193
194, 195
196, 197
198, 199
200-202
203
204, 205
206
207
207-209
209, 210
210
210, 211
211 , 212
212, 213
2 1 3 , 214
215 , 216
216, 217
23 7
217
Phys ika l .
Zei tsch.
*
...
. . .
...
...
. . .
...
1
2
3
4
5
6
7
8
9
10
11
12
13
14
1 5
16
17
18
...
Proc,
Oh em. Soe.
Proc.
R oy .
Soc.
ttee.
T r a v
Chim.
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2 3
24
2 5
26
27
28
29
30
Pub l i ca t i on
of m a t t e r
of scientific
in t e r es t now
a b a n d o n e d .
4 7 , 4 8 , 49
4 9 , 5 0
5 0 , 5 1 , 5 2
5 2 , 5 3 , 5 4
55 , 56 ,57
5 7 , 5 8 , 5 9
59 , 60
6 0 , 6 1 , 6 2
6 2 , 6 3 , 6 4
6 4 , 6 5 , 6 6
6 6 , 67
68, 69
69 , 70
71,72
7 2 , 7 3 , 74
7 4 - 7 6
A. 77 ,78
7 8 , 7 9 , 8 0
8 0 , 81 "
8 2 , 83
83 , 84
8 4 , 8 5 , 8 6
86, 87
88 , 89
8 9 , 90
. . .
9
10
11
12
13
14
15
16
17
18
19
20
2 1
2 2
23
24
25
26
27
28
29
30
31
32
33
34
35
36, 37
37
38
Si tzungaber .
K. Akad .
WISH. Wien.
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
Stah l
u n d
E i sen ,
AVied.
Anna len .
10
11
12
13
14
15
16
17
18
19
20
2 1
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
3 9 - 4 1
4 2 - 4 4
4 5 - 4 7
4 8 - 5 0
5 1 - 5 3
54 -56
57-59
60-63
64 -66
67-69
C o n
t i nued as
Aimalen
dor
P h y s i k .
Zei tsch,
ana l .
C hem.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
Zei tsch,
ai igew,
C hem.
3
4
5
6
7
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Zei tsch.
a n o r g .
C hem,
1,2
3,4,5
5-7
8-10
11, 12.13
13-15
16-19
19-22
2 2 - 2 5
26-29
2 9 - 3 3
3 3 - 3 7
3 8 - 4 2
4 3 - 4 8
4 8 - 5 2
52-56
56-60
61-65
6 5 - 6 9
6 9 - 7 3
73-79
7 9 - 8 3
8 4 - 9 0
9 0 - 9 3
94 -98
9 9 - 1 0 1
102-104
105-109
Ze i t sch .
E l e k t r o -
C hem.
Zei tsch.
K r y s t .
Min .
1 ,2
2 , 3
3 , 4
4 , 5
5 , 6
6 , 7
7
8
9
10
11
12
1 3
14
15
16
17
18
19
20
21
22
23
24
2 5
1 6 , 1 7 , 1 8
19, 20
20, 2 1
2 1 , 22
2 3 , 24
24, 25
26-28
28 , 29
29-31
31 , 32
3 2 - 3 4
34 -36
36 , 37
37-39
39 , 40
4 0-4 2
42 , 4 3
4 3 , 44
4 4 -4 6
4 6 , 47
48 , 49
49 , 50
50-52
52, 53
54
55
N o
issue*
Ze i t sch .
phys ika l .
C h e m .
89, 90
91 , 92
92
92
* R em aind er of vo l . 55 appea r ed i n 1920 .
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*
A TEXT-BOOK OF
INORGANIC CHEMISTRY.
VOL . X I . PA R T I .
ORGANOMETALLIC COMPOUNDS.
C H A P T E R I .
O R G A N O M E T A L L I C D E R I V A T I V E S O F T H E
E L E M E N T S O F G R O U P I.
T H E t h r ee e l emen t s l i t h ium, s od ium, and po t a s s ium bea r l i t t l e r e
sem blan ce to copper , s i lver , an d go ld in the i r inorg an ic de r iva t ives ; bu t ,
w i th t he excep t i on o f go ld , t hey s how mor e r e s emblance i n t he i r o r gano -
m e t a l l i c c o m p o u n d s .
L i t h iu m , s od ium , r ub id iu m , and caesium f o r m two t yp es of com
po un ds , (1 ) RM , (2 ) R
3
CM , wh i l s t po tas s ium on ly g ives ty p e (2 ) .
L i t h i u m a n d s o d i u m d e r i v a t i v e s of t y p e R M a r e p r e p a r e d b y t r e a t i n g
the co r r e s pond ing mer cu r y a lky l s o r a r y l s w i th t he me ta l i n d r y benzene
or l ig ro in . R ub id iu m an d caes ium, how ever , a re ob ta in ed b y in te rac t ion
of t h e m e ta l an d zinc a lky l s . L i t h iu m m e th y l is be s t i s o l a t ed f r om
l i t h ium e thy l and mer c u r y d im e th y l i n gas o li ne s o lu t i on . Th e mos t
s t r ik in g pr op er ty o f th es e m eta l s i s the i r a ff in ity fo r oxy gen , an d th i s
p r ope r ty i s a l s o exh ib i t ed i n t he i r o r gano compounds f o r t hey a r e i n
flammable in a i r . Th e l i th iu m co m po un ds a re m ore c ry s ta l l in e th a n
those o f sod ium, bu t the l a t t e r a re more inso lub le in ind i f f e ren t so lven t s .
I t i s in te res t ing to no te tha t whi l s t l i th ium and i t s inorgan ic sa l t s co lour
the f l ame red , l i th ium phenyl burns wi th a ye l low f l ame.
Sch lenk and Marcus in 1914
1
f o u n d t h a t t r i p h e n y l m e t h y l c h lo r id e
r e a c t e d w i t h s o d i u m a m a l g a m i n d r y e t h e r so l u t io n , w h e n t h e o p e r a t i o n
was ca r r i ed ou t in an a tm os p he r e of n i t r ogen . Th e r e s u l t i ng com
p o u n d , s o d i u m t r i p h e n y l m e t h y l , w a s a b r ic k - re d m a s s , d e c o m p o s e d b y
m o i s t u r e o r c a r b o n d i o x i d e . K r a u s a n d K a w a m u r a i n 1 9 2 3
2
s howed
t h a t t r i p h e n y l m e t h y l c h l o r i d e r e a c t s w i t h s o d i u m a n d p o t a s s i u m i n
l iq u i d a m m o n i a , b u t t h a t t h e p o t a s s i u m c o m p o u n d is m o r e s t a b l e t h a n
th e s od iu m de r iv a t i ve . A nu m be r of com pou nds s imi l a r i n s t r u c tu r e
to t r i pheny lme thy l have s i nce been s hown to g ive s imi l a r r eac t i ons .
R ub id ium and c se sium a ls o f o r m s im i la r de r i va t i ves .
3
Copper , s i lver , and go ld a re con t ras ted wi th the th ree fo rego ing
1
Schlenk and Marcus, Ber., 1914, 47, 1664.
2
Kraus and Kawamura , / . Amer. Chem. Soc, 1923, 45, 2756.
3
Grosse, Ber., 1926, 59, 2652.
3
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4 ORGANOMETALLIG COMPOUNDS.
elements in being stable towards ai r , water , and some acids, and in these
respects bear some analogies to the metals of Group VIII . In organo-
metall ic chemistry this l ikeness is only shared by gold, since this is the
only elem ent th a t forms stable com pou nds . Copper and silver phe nyls
have been repor ted by several inves t igators , bu t they are very unstab le
com poun ds an d l i t t le is known a bo ut thei r general beha viour . I t wi ll
be noted that this instabi l i ty is shared by the phenyl der ivat ives of the
alkal i metals .
Gold
1
forms two tervalent types of compounds , R
2
M X a n d H M X
2
,
b o th of which are fairly stable solids. T yp e R
2
MX shows the analogy
between gold and thal l ium, the lat ter metal giving only this type of
organic co m po un d; m oreover, no m on ov ale nt der ivat ives of gold or
thal l ium h ave been i so la ted . D iethyla ur ic bromide is prepa red by the
interact ion of auric bromide and magnesium ethyl bromide, and this
substance i s changed to the second type by t reat ing i t wi th bromine in
chloroform solution, the halogen replacing one of the ethyl groups.
Both compounds precipitate si lver bromide from solutions of si lver
sal ts , and the diethylauric bromide forms an addi t ion compound with
am m onia , when wa rmed w ith i ts aqueou s solut ion. No aryl der iv at ive s
of gold have yet been obtained, al though when isolated they will be
found to be qui te s table, and probably have no mel t ing-point below
300 C., l ike the corresponding thal l ium compounds.
L I T H I U M .
2
The l i thium alkyls resemble the sodium alkyls in being colourless
compounds , but are cont ras ted to them in being to some extent
crys tal l in e. W ith th e exception of th e difficult ly soluble l i th ium m et hy l,
they are readi ly soluble in benzene without decomposi t ion.
L i t h i u m m e t h y l , L i CH
3
or LiMe.When a benzene solut ion of
l i thium ethyl and a gasol ine solut ion of mercury dimethyl are mixed, a
white microcrystal l ine powder immediately separates , in accordance
wi th the equa t ion :
2 L iE t + H g M e
2
= 2L iM e + H g E t
2
soluble soluble insoluble solub le.
In the dry state the compound is completely colourless, in air i t inflames,
bu rn ing w ith explosive violence. Th e flame is red and ac co m pa nie d b y
a shower of yellow sparks.
Lit h ium e t hy l , L iC
2
H
5
, i s prepared by the interact ion of mercury
die thy l an d m etall ic l i thiu m in ben zen e or l igroin solution. I t forms
thick, clear , hexagonal plates , mel t ing at 95 C. in a ni t rogen atmo
sphere ; at higher tem pera tures vo lat i li s ing an d condensing in th e cooler
pa rts of th e ap p ar at us in drops, w hich soon solidify. I t is somewhat-
soluble in benzene or gasoline, but when exposed to the air the body
inflames and burns with the red l i thiu m flame. Li th ium ethy l reacts
wi th t r i e thy l -n -bu ty lammonium bromide to give t r i e thy lamine and
d ie thy l -n -bu ty lamine , and wi th t e t r ae thy lammonium bromide to g ive
e t h an e an d e t h y l en e .
3
L i t h i u m n - b u t y l , L iC
4
H
9 s
w i t h t e t r ae t h y l amm o n i u m b ro mi d e
1
Pope and Gibson, Tram. Chem. Soc, 1907, o i, 2061
2
Schlenk and Holtz, Ber., 1917, 50, 262.
3
Hager and Marvel, /.Amer. Ghem. Soc, 1926, 48 , 2689.
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y i e ld s t r i e th y l a min e ; w i th t r i e th y lb e n z y la mmo n iu m b r o mid e i t g iv e s
d i e th y lb e n z y la min e ,* w i th t r i - n - b u ty l - n - h e p ty l a m m o n iu m iod id e i t
fo rms d i -n -bu ty l -n -he pty lam ine . Th e fo llowing reac t ions w i th l i th ium
n-bu ty l have been ca r r i ed ou t ,
1
the reac t ing subs tance be ing g iven f i r s t
and the produc ts of the reac t ion shown in bracke ts : n -hepty l b romide
(n -undecane ) ; me thy lene iod ide (n -nonane ) ; / ? -b romos ty rene (pheny l -1 -
he xe ne - 1 ,
trans-trans i somer o f d ip hen y l - l -4 -bu ta d ien c - l -3 (? )) ; t r i
phen y lch lo rom e than e ( t r iphe ny lm e thy l pe rox ide , t r iphen y l -1 : 1 : 1-
pe n t an e ) ; o -, m- , p -b ro m oto lu ene ( to luene ) .
L i t h i u m i s o - a m y l ,
2
L i C
5
H
l l 5
r e a c t s w i th t r i e th y l - n - b u ty l a mmo n iu m
b r o mid e t o g iv e d i e th y l - n - b u ty l a min e a n d l i t h iu m n - h e p ty l , w i th t e t r a -
n - b u ty l a mmo n iu m io d id e t o f o r m t r i - n - b u ty l a min e , a t r a c e o f a h y d r o
ca rbon and poss ib ly n -hep tane .
L i t h i u m p h e n y l , L i . C
6
H
5
o r L iP h ,
3
may be p repa red f rom mercury
d iphen y l and me ta l l i c l i th i um o r l i th ium e thy l and mercu ry d ipheny l .
In the dry s ta te i t i s a pure whi te , microcrys ta l l ine powder , which burns
in a ir w ith a yellow f lame, n o t a red l i th iu m flame.
L i t h i u m t r i p h e n y l m e t h y l , L iC Ph
3
,
4
is p re pa red by t rea t in g 1 m ol .
of t r iph en y lm e th y l ch lo r ide in anhy drou s e the r w i th 6 mols . of l i th ium hi
th e form of 0-5 pe r ce nt , am al g am , in a specia lly design ed f lask. I t is an
o range - r ed powder and fo rms a s tab le e the ra te , L i .CPh
3
. 2 E t
2
0 . W h e n
ac ted upon by wate r in the absence of a i r i t decomposes accord ing to the
e q u a t i o n :
L i . C P h
3
+ H
2
0 = L i O H + C P h
3
H
S O D I U M ,
Th e firs t a t t e m p t to ob ta in sod ium a lkyl s was due to W ank lyn ,
5
but his
work only led to the format ion of sodium-z inc-e thy l double compounds .
Schor igin
6
was a lso unsuccess fu l in ob ta in ing p ure pro du c ts , whi ls t
Acree
7
descr ibed a body which he cons idered to be sodium phenyl , bu t
th i s was a f te rwards r e fu ted by Hi lpe r t and Gru t tne r .
8
The sodium a lkyls in the pure s ta te a re co lour less , amorphous , in
so luble pow ders , in ind i ffe ren t so lv ents . Th ey decom pose w hen hea ted
to th e m el t ing-po in t . T he y a re ex t rem ely inf lamm able in a i r, th e in
flammabili ty decreas ing w it h r is ing m olecu lar w eight of th e a lkyl
res idue s . Sodium oc ty l i s susce pt ib le to oxy gen , la rge par t ic les ign i t ing
in air .
9
S o d i u m m e t h y l , N a C H
3
or NaMe.Sodium chips a re p laced in dry
l igroin (B.pt . 80 C) , and a l l a ir d isplaced by dry, oxygen-free ni trogen.
Th e r equ is i t e am ou n t of m ercu ry d im e thy l is th en adde d and t he
te m pe ra tu re m a in ta ined a t 65 C . Af te r s eve ra l days th e p ro du c t is
ob ta ined a s a wh i te powder .
S o d i u m e t h y l , N a C
2
H
5
, i s p repared in a s imi la r manner ,
1 0
b u t t h e
1
Marvel, Hager, and Coffitnan, J. Amer. Ghem. Soc, 1927, 49 , 2323 .
2
Hager and Marvel , he. cit.
s
Schlenk and Holtz , Ber., 1917, 50, 262.
4
Grosse, Ber., 1926, 59, [B], 2652.
5
Wank lyn , Annate** 1858,107, 125 ; 1858, 108, 6 8 ; 1859, i l l , 234=;1866, 140, 211 .
6
Schorigin, Ber., 1908 ,41 , 27 17 ;
ibid.,
1910 ,43 ,1931 .
7
Acree, J. Amer. Ghem. Soc, 1903, 29, 590.
8
Hilpert and Gruttner, Ber., 1913, 46, 1679.
3
Schlenk and Holtz , Ber., 1917, 50, 262.
See Schorigin, Ber., 1910, 43, 1931; ibid., 1923, 56, [B], 176.
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OEGANOMETALLIC COMPOUNDS.
react ion is com plete in one to two ho urs. S o d i u m p r op y l an d n - O c t y l
have also been obtained.
S o d i u m p h e n y l , N aC
6
H
5
, formed from m ercu ry diphenyl , exh ibi ts
the same propert ies as the alkyls .
S o d i u m b e n z y l , C
6
H
5
.C H
2
.Na. Unlike the preceding compounds,
sodium benzyl is isolated as an intense red, crystal l ine powder, in
soluble in benzene or ligroin, but fairly soluble in ether, to which it
im pa rts a deep , reddish-yellow colour. T he eth erea l solution will con
duct the electr ic current , showing that the metal l ic atom is l inked by a
ca rbo niu m va lence . It inflames in air, b u t if th e oxidatio n is slow,
m uch st ilbene is formed. D ry carbon dioxide conve rts i t in to sodium
phenyl aceta te .
S o d i u m t r i p h e n y l m e t h y l , P h
3
C N a .
l
1 . Ten gram s of t r i -
ph en ylm eth yl chloride in 500 c.c. of dry ether are t re at ed with 200 gram s
of 2 per cent , sodium am algam , and the m ixtu re shak en on a mach ine for
one to tw o hou rs. D uring the operat ions al l ai r m ust be replaced b y
ni t roge n. A solut ion of sodium tr ip he ny lm eth yl is thu s obta ined in
quant i ta t ive y ie ld .
2. Ten gram s of sodium powder are am alga m ated with 10 grams
of mercury in 200 c.c. of dry ether, the reaction being carried out in
ni t rogen . Triphe nylm ethyl chlor ide, 2 to 3 gram s, is th en int ro duc ed,
the substances mel ted and put on a shaking machine, the react ion being
com plete in twelv e hours. A dark orange-red solution is ob ta in ed ; th e
ether is evaporated and the residue t reated several t imes with petroleum
ethe r an d eva pora ted unt i l a sol id is produc ed. All m anipu lat ions are
carried out in nitrogen, since air , moisture, or carbon dioxide cause
decom posi t ion. The compound forms a br ick-red m ass.
2
3. Sodium tr ipheny lm ethyl m ay also be prep ared from tr ip he ny l
methyl chlor ide and metal l ic sodium, when the two are al lowed to react
in l iqu id ammonia , and the hydrogen a tom of t r iphenylmethane i s
replaced by sodium in about an hour.
The compound is very react ive, even at the temperature of l iquid
am m onia. W ith water i t reacts to form sodium hyd roxid e and t r i
pheny lmethane ,
H i
s
C N a + H
a
O = P h , C H + N a O H
By the action of oxygen, a white product is formed, the composit ion
of which has no t been determ ined. The react ion w ith am m on ium
chloride hi l iquid ammonia is probably represented by the equat ions,
P h
s
C N a + N H
4
C I = P h
8
C N H
4
+ N a C l = P h
3
C H + N H
3
+ N a C l
The in term ediate amm onium compound is not i so la ted . Am m onium
hydroxide wi th sodium t r iphenylmethyl y ie lds t r iphenylmethane and
sodamide, and sulphur dioxide forms sodium tr iphenylmethyl sul-
ph ina te .
Sodium tr iphenylmethyl is moderately soluble in toluene or benzene,
but insoluble in petroleum ether and l igroin.
The fol lowing are typical react ions of sodium tr iphenylmethyl wi th
certain organic compounds :
1
fcchlenk and Holtz, Ber.
t
1916, 49, 603; Schlenk and Ochs,ibid., 1916, 49, 608;
German Patent 292310 ; Kraus and Kawamura, J. Am er. G hem. 8oc1923 45 2756
2
Schlenk and Marcus,Ber.,1914, 47, 1664.
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W i th t r i p h e n y lm e th y l c h lo rid e , h e x a p h e n y le th a n e is p r o d u c ed , t h e
reac t ion be in g car r ied ou t in l iqu id am m on ia . Th us :
P h
3
C N a + C l . C P h
3
= N a C l + P h
3
C . C P h
3
Simi la r ly wi th d ich lo rod ipheny lme thane , a mix tu re o f hexapheny l
e th a n e a n d p e n t a p h e n y le th y l i s f o r me d .
1
W i th b rom obenz ene , u s ing
the above so lven t , c a rbon te t r apheny l r e su l t s ,
P h
3
C N a + P h B r = N a B r + P h
4
C
With methyl benzoa te , ^8-benzpinacol in i s formed in accordance wi th
the equa t ion :
P h
3
C N a + P h . C O
a
M e - P h
3
C . C O P h + N a O M e
If methyl p-ch lorobenzoa te i s used , p -chIoro- j8-benzpinacol in i s
ob ta ined . S ince sod iu m t r ip he ny lm e th y l shows a t en de nc y to exchange
i ts sod ium a to m for hy dro ge n , i t ca nn ot be used for con den sa t ion s w i th
subs tances which can func t ion in enol ic forms , such as e thy l ace ta te .
Wi th a ldehydes , e thano ls a r e ob ta ined , f o rma ldehyde y ie ld ing t r i -
p h e n y l e th a n o l ,
P h
3
C N a + O C H
2
- P h
3
C . C ( O N a ) H
2
In th e ca se of ben za ldeh yde an d fu r fu ra ldehyde , t e t r a ph en y l e thano l
an d t r ipheny l fu ry l e than o l a r e i so la ted r e spec t ive ly .
W ith ke ton es as w i th es te r s , tho se w hich a re cap able of ex is t ing in
enol ic forms ca nn ot be em ploye d , and d ia ry lke to nes y ie ld no cond ensa
t i o n p r o d u c t s , e.g.w i th benzo phen one , an e th ano l is no t fo rmed , bu t th e
so lu t ion becomes green , s ince meta l l ic ke ty ls a re produced , accord ing to
the equa t ion :
P h
3
C N a + C O P h
2
^ P h
3
C , C P h
2
. O N a
With d ibenza lace tone , t e t r a s ty ry lp inaco l in i s f o rmed .
S o d i u m p h e n y l b i p h e n y l y l - a - n a p h t h y l - m e t h y l ,
P h . , C
1 0
H
7
> C [B ], 93 1.
2
Krause , Ber.
t
1917, 50, 1813.
3
L6hr, Annalm, 1853, 87, 55 .
4
Wank lyn , Quart. J. Chem . Soc, 1856, 9, 193 ; Jahresber., 1856, p. 554
5
Frank land , Annalen, 1859, i n , 62.
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2S ORGANOMETALLIC COMP OUND S.
w itho ut cooling. W hen th e reac tion is com plete, th e m ajority of th e
eth er is distilled off in a stre am of nitro ge n, u sing a frac tion atin g co lum n,
an d a te m pe ra tu re not above 80 C. Th e residue is distil led from an oil
bath, in ni t rogen, at a pressure of 13 mm., the ether and cadmium
m eth yl being collected in a receiver cooled in liquid air or ca rbo n diox ide-
eth er m ix tu re . After one hour th e te m p er at u re is raised to 120 C.
The prod uc t is fractionated to remov e th e ether, the n distil led in n itrog en
at ord inary p ressure. At 105-6 C. 60 gram s of pure cadm ium m eth yl
are ob tain ed . Yield 85 per cent. W hen po ured into w ater i t s inks,
evolving methane and giving a precipi tate of cadmium hydroxide.
When cooled it solidifies, melting at 4-5C , the crystals ta kin g the
form of star-shaped rods when the product is disti l led under reduced
pressure into a receiver cooled in liquid air.
The following cadmium alkyls may be prepared in a similar manner,
the yields being shown in each case:
C a d m i u m d i e t h y l , 90 per cent. ; c a d m i u m d i - n - p r o p y l , 85 per
cent. ; c a d m i u m d i - n - b u t y l , 70 per cen t . ; c a d m i u m d i - i s o b u t y l ,
75 per cent. ; c a d m i u m d i - i s o a m y l , 55 per cent.
The physical constants of these compounds are shown in the
Appendix, Tables II . and III.
C a d m i u m d i p h e n y l , CdPhg,
1
may be obtained by heat ing metal l ic
cad m ium and m ercury diphenyl in an atm osp he re of hy drog en. I t is
s table in the dry s tate, but becomes discoloured when kept in a vacuum
desicc ator for an ho ur. W hen air is passed th ro u gh its benze ne solutio n
several colour changes take place, and a reddish-brown body is finally
pre cip itated . W ith water the brown solution is decolorised an d
cadm ium hydroxide precipi tated. Cadm ium diphenyl quickly de
colorises iodine solution, and the cadmium maybe replaced by mercury
or zinc with formation of mercury and zinc diphenyl.
1
Hi lper t and Gri i t tner , Ber.t 191 3, 46, 1(575.
*
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CH A P TER I I I .
M E R C U R Y .
A L K Y L C O M P O U N D S O P T H E T Y P E S R
2
H g A N D R H g X .
T H E ea r ly workers on the type R
2
H g p repa red the i r com pounds by
m ak in g use of d i lu te sod ium am alg am s. The a lky l iodides were shake n
w ith an excess of s