newton - a textbook of inorganic chemistry vol xi organometallic compounds part i

8/11/2019 Newton - A Textbook of Inorganic Chemistry Vol XI Organometallic Compounds Part I

1/437


2/437

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


3/437

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.


4/437


5/437

*

Printed in Great Britain by

NEI LL & Co. , LTD . , ED I NBURGH.


6/437

*

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

vii


7/437

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 ,


8/437

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.

*


9/437

*

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.

x i


10/437


11/437

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.


12/437

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


13/437

*

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


14/437

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.


15/437


16/437

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


17/437

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)."


18/437


19/437

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.


20/437

J

C

O

O

O

c

c

*

to

^

e

c

e

a

&

V

0 11 o

39-42

Year.

Phil.

Trans.

s

o

M

S

S

2

3

P

B

P

o

o

S

uar

Chem

E

Q

"

o

e

c

*

Rec.

Trav.

Chim.

>

d

^

^


21/437

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


22/437

>

_

^

j

^

3

W

^

^

2

J.

Physical

Chem.

-

r

=

2

S

-

f

S

H

S

Q

t

~

NC

^Q

S

r

H

e

C

o

0

O

-

V

-

S

I

Q

H

C

O

N

O

l

'

^

^

^

T

^

J

C

*

#

o

O

C

C

C

M

C

H

M

I

O

N

C

M

C

C

C

C

O

C

^

C

m

0

t

o

o

t

o

>

O

C

T

C

C

>

O

1

r

r

1

O

i

-

H

M

C

^

C

C

C

M

C

C

O

C

M

i

D

O

^

i

>

0

0

a

0

C

C

C

C

C

f

l

i

1

1

1

O

c

r

N

K

C

O

M

O

)

C

C

C

C

C

O

r

M

C

^

a

0

a

e

0

C

*

t

O

1

C

O

f

O

N

C

O

O

O

H

r

r

H

i

H

C

C

1

o

*

c

o

C

C

C

C

C

C

C

C

O

-

^

O

O

O

1

C

C

C

C

C

1

1

1

1

1

I

T

O

C

r

H

O

O

O

O

r

H

C

C

C

C

C

1

o

c

O

O

O

O

O

O

Ci

H

C

T

O

C

O

H

C

Q

I

S

O

i

t

o

o

o

o

t

o

^

m

N

c

o

C

#

t

o

C

O

r

H

i

H

H

r

C

r

H

C

O

1

O

r

H

r

H

r

r

H

i

H

C

O

C

^

t

O

*

0

C

C

C

r

o

c

x

J

>

C

C

C

C

C

C

O

C

C

C

C

C

O

H

I

M

W

*

0

C

C

C

C

k

T

J

N

X

C

1

H

1

H

r

H

C

C

C

C

C

O

r

H

C

C

O

O

O

O

O

ar

C

M

^

C

O

C

t

*

>

>

1

0

I

H

c

L

o

.

O

*

>

J

-

O

O

r

H

M

C

r

^

r

i

-

r

H

C

O

0

O

C

C

C

M

C

H

C

N

C

S

C

C

C

C

C

C

O

O

C

N

T

H

0

o

o

o

a

J

O

H

C

W

0

0

o

o

a

N

c

o

r

o

o

H

C

M

C

C

C

W

N

0

O

C

M

C

C

O

r

H

C

C

T

H

C

C

C

M

C

C

C

C

C

C

m

t

o

0

a

O

O

O

O

O

a

r

(

M

^

t

C

0

O

C

0

0

O

O

H

C

O

W

N

Q

C

C

O

C

0

C

N

1

H

i

H

H

i

H

C

0

#

O

C

H

-

C

O

O

0

5

M

"

>

f

O

C

^

t

O

C

O

O

O

O

O

l

H

r

i

H

H

t

>

a

H

c

o

O

O

O

O

O

rH

H

H

M

C

C

O

C

C

C

C

C

O

r

H

C

C

#

*

^

^

^

*

i

n

o

c

o

C

C

M

C

C

C

C

C

C

C

O

i

-

H

M

C

#

H

H

H

H

H

a1

0

C

C

O

O

i

H

I

H

r

C

O

M

O

r

H

r

H

1

H

r

r

H

1

H

r

H

s

a

H

M

0

C

j

O

H

r

r

r

^

i

H

H

r

H

r

H

N

O

O

C

f

O

r

C

C

C

-

m

t

o

J

0

o

^

^

^

^

^

I

T

O

*

>

O

r

r

H

i

H

r

r

H

Or

H


23/437

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 .


24/437


25/437

*

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


26/437

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.


27/437

ORGANOMETALLIC DER IVATIVES OF ELEMENTS OF GROUP I. 5

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.


28/437

6

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.


29/437

ORG-ANOMETALLIO DERIVATIVES OF ELEMENTS OF GROUP I. 7

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.


50/437

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.

*


51/437

*

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

newton - a textbook of inorganic chemistry vol xi organometallic compounds part i

Documents