Acceptor properties of halides of elements of groups IV and V

IV

v·

8 D ee

i

!)''I ,~,,

,q

wi s to to

also

1

INTRODUCTION

₃

IV H

₉

4"

Otl

OF

v

21

r·

.) OF

v

I H. DiBCUS

II

₄₇

Go

IDYL

IV

I Hesults Discussion

II

₇₃

7 ..

l>ipy'

substitut

.. l>ipy 0 Most the c:r•ystalline are

1

in nitr

as to

vvi tl1 an

s

..

D

t

Wi tb vai'ious or

R ,.Fl:nX₁ ..

It. ~-:n

nitr

sli ionisat is

tht1 tin

s :r• t

~ but t

Fl witrJ tvw

)"'? :L'

t

crns, T(

1J'Jith all

exes

, whi

to ionise in

are

e..

:n

1V

to

all tion

i

an

l1it I'

It if; Ol:'

<: tin

t;

t

t littl('J j(J

t ( )

t

o:r t 1

n.

1t

of'

')

11 1:i i l l

I '

.

)

l) 011

!·

1

:i .

(1

(

)

f'l ) \ J I 1

( ~1)

(1J )'

+ u

lJ

,,

>)

iB

it.

i

(

ac

mo.;jrn•

1

q n:lt,:to:nH"' t\

l.

On tho

tlt it lG 11

len'

lf1

n1

'· en•

t•

th Jt ~j

l i

)

tion~ f\

lJrl f3

l

"

,,

·1, IJ

h.:t

·I· _lo ;:j

c):e t

1 :1 :1. ::-~tx•

J.

l.•

1

, ..

1 A i 0 1 1 1 1 ,J. \o r;.., J it adcltwt:.::; "" .:J (a) 1. (n) t

on OonoP

.has

Ot!l' of t

6

:i L lf,;

)1

"'T

t j ~"'

1\

r\

.. :;

~~1 J? (~

i.

t

i l l l

01'

t.o

ntltion. b

i l i

It;

to

e1i1 .. to

to

r

•

b

ions evon }Jon a

it

Gil nrJJl t

cu.t

t -~ aB ~bll t

'1

ClXEJS Of' th.o

8a.·G iC)fl

t.

1i

~)()

or•!

t.o tll tin

tc:

1B 1

1 eD 11

1 i

1 (]t111B

It

io:n. t

to to

[J (_) _t t of _g:ll. ouo

ox

omi

cl

on

r :tt in

to

ammo-0!'

or

1

Of'\ -l-'1 b.J u

eon :i. nn

:r

t, i (:3

c po lo t 1 tlon

r:.ts et t

( i

0

t

c

J1

)

u

t.:ion

J?nact;s

~~·

.J , oJ:1.<l t e s :l

nip t~) I) " ,., ~::' _J

-Lt .

. ~\·

~'n"l.t' to 'be

sor

:i.

11 i

salt ( i ₀ ) •l• G _I

10

l;y

:icon

c:lilic;on

Fl t..ho :fo:r•(nu ti.on

f3()

nilie\)n t

6 _{to f'o.t•in}

0 s

nr-; _"' >:> te)

t tlJ.O ta~

E38 ... ~. u :tt iB

II

() sil:t

7

is

1

C!Eftl0()

:i

"~.

'·'

t

c~ DO boon

t an

:l

B are ii10l' e 1

0 (! :i :ls

I) _ts

t.

tl

ail

to

l i

no I'

roonorner i C\

Ii:; is

an

ll

<J

) 1

£]()

(4

•. J

12.

t

f.:J of

c

t)O

c,U

'

o:p~,n·

nnd.

t

11 l)CJUZ

:nul

"

um

0

1c

mo

(~

·'

on an i indie:.1t

ae >.'011 an

v.ri

I. t.

t _{" '·'} c):e

unci.

tG not CJ

the t.

fluorosilicates.

()JlB n.I~ () tJ 1 t:~ 1. J

ion.

or:tc acic1 o ntion,

lith

ot'

t no

g _m.11con

\:'l(l

ll i Yt_~;

L (;

tE)Cl

1

ionn

t no

i:o.

c~

~l

c

.e

t

:1.

1 a t

t (

Yl~1t~ as (

18 morn 1 Th.lB :ls f]

:tp a.~t~ EJS 1 t

t

t:ton :r•

(

lloon

or• ]J j.

I'

l;o

15"

icm t1n1l. t

a 1 ~1

B i

t)

OJ.'

j,-t

CH1 quat )

has VCH'

atom

Oin.

fluor•

sol

COWJ'r::t.t ib1o rd

:I.e tiJPCQ

bnt itn :iB

ave

r:rtJFJ.11

ol' pr

~· :t 8

1 a

been c!oru3

'l'l'Ot

.l' '::'\ _{G\ .• •}

n.t

u t.o

til t

1

i

lb

t

i , .. ~)

an

:l1 it~,r

V1_:l.t1 no

to n:l.tl1

t,

CLtt

8

r;

i

that.

cat ion V:ilti

o1yte

(:1

Lo cl

.. IT \

cLonu:r:' t, .. , J

Elt!J.cij.

Q! 1 i; :in

L) + :nJ

c:~v

+

n

1

1'1

, tt iB

f"ll1

oct ln a

an

/\

on.

ton

:in. t oscrwo

til

l i

t,lorw t

j_

(H

_).:n

f'il'

ear t. SCt

oven_ in.

ti.n t

~:1:re

in

I'

(

70

0

I"'

1 •J t

eno on

:t•

:C01? t [1

v:LEl\'1 of' CC)'llf3 0

0 t ; :tt.

1

of n :is

1 11

"

to

a:r1c1

1

\)icc

77

r

t

lat :i

ilti".l\l"i011i i iri ot

t Vii

n.

o rna

( 1 )

ors,

( ) c

hrll

o:ne or mot:•o iono

hn1

or·

( ~) nit.

in

c

0 i ic

COOI'dl

c:r•o :I.e :t'

[j() t11

tn n 11

ut:l1 DO

I'OHB osont

n ₉ S'U

i l l FH)

ion r•csontJ:nco Jth

tcJ

h thcd.:t:'

q

lf

::?./

f' '7

/)

t. 0

io ns in

and. D

tux•o

unu:::n.1

is

o:ns

i 1

i.s 0!'101':1 f'OI'

I J: J1

'l'.h 0 i

i

0 J.'

t

t:J. 1 1

r•

1o

ence

a 1 : 1 flO

on. tcJ

n ol 01'\ltl a torn,

i\• j , '

c

to

i a:r:•o

neon ion iFJ ra , a:nl.l

t :i..'L :fn.ll.D

I'

tB n. t:iJUJ1 t

t11 0 '1

BOI'VCci. no .1.

i

L< i

J:'OOJI! ~· u nr b /\ 11

t;:r> ifl uor• a 'l

tt

ion~

n . .~•e of t~h.o

<J in [l onn

Fl o:o.e pho I :::~ P

:J

.'J cy

/\11

Dl1

t.o :t

..t

\.>

('1

a1 :J

to

()

11 1: 1 ad

'tlCJ

1

tcm to tho

s-1

.,

u

t.o

IIJ B and

tl ar

an

i :tt

lt .!. L

I> !_, 1\

nm

1 :i

"

J

en

A. 1

enel1:i t. ee

·1 ~. 1 COUT)10 t.1

non-ni trobo:n:~enc and norm~;:tl mol ocular

:ln thiG Bolvent ~ In. c:ontrast wit;'ll t.l1io tiH: t.r:· i:i.ot't

a molar in

ni"cx•o-ionisation as (Asi₀

.D)+r-,

and

<-- ton confirmed this by

acid th.e ccn'l'CDpo:ndir.tg [.Jex•ch1o:t•a.te 'lH:ll':> formerJ,

conOJtetivity of

evidence of the r

methylhalo~enoarsines tort ph.o 1 01 ~ 1 o::2 _"

a series of these c

that the salts of gr est stahilit were

b triethylpJ:wsphine n.nd. :toclor:u•s

·vex1 only for>

complex ~tJ"a.s al~3o form.ecl bctvmen dimethyl BitlfJ

The existence of cations of t

suggested_ b;'l t

(

2'1

o:r• a.t 1

1 t :i S I! C) iJ

tt:~:r•e

flB (~():£tUiB~t

OJ.'

OX'

i e

1

VI:lth

:Ul l;IJ'

has 110

1'0

np; to ion

i

1

₃

j) G

1

~j 1

e 1:) f'

FJC)fT!O iE;D_tlon₁₁

)~

i

10 II -'T J. lJ

A

ln

nate

thE~ tYJO

.

om l.!:'i

119

l l

a.l 1 (

0

e oi'

..

A

VJit

A.s

el

(

lo

, n.s is

' :e

at

L'lll111 t:r1ch1m:

, l\ 1

1 '

'

iono

it i

101 ) _,

-~ .:>

1

COJ:'r.e

a hr

i

(

1

1

8

to be

n

e

non.-(1.,. X )' '.,J.,_, ..

~)

c

31

no

It :lG t and. 8 SGOC

B are f'oi•med 'b s nncl

G(J OCCIU' !flOI'e

l.onco

iotHl

At

t.U'

1J

bl

It

1

A-iJ

fJ() ₁

i t. o:n noltlt;

an i rtOI' 'L

O<)l t ~

mea.m.u•

/\11

I 11 s

solu1lil eno.

CJ i ( b n (1.Jtt1f'3

ni

en

I

19

0 ' )

e:M 9 ~)

'1 0 n u 1 ~) ;Wo9

f' ₎ (e.) _)J,, (1J)

( 13,)

n :lo

\

O~ '5 '1

)

1 ₎

H:i. f});:(Jf3

1 (

3 :; .. 0 ( ) 0 () (_::,

lson9 ar• ivltios t.h

t

ne,

ib

ni

C< ( ()1.,1 '!.)

!-:,.) f--) ,,J ~"'). t

c. )I

om.

ihi1

is c ZOB tiot::;

e 1:i.c l' th

smut.IJ t r i i r:ll' c so

'I'ho ('

t. t-lfl 1C)11t

1

( ) f) ' c+ ) ·+·

L

be on

:t c;: 1J (JClf:lllf3G

1o~r so1nb:l.1i t

Ol:' t it1cy1

ti

El 1 itcd c:onc

iOil ~

i 1 )

i.

In

(

t ( 'i' \, ·t· ' ~

i

;

11:1 rnnnnor•0

(Ph

(n

r:rva:U

:i. ()(l.

)·:·r- + 1 ,, -~~,>

(

t. ..

A

=1

111

f )

c.

-1

A

iEi

on

ion

)+I ·z

.• )

tU'O :0101'0

t~he

3b

.

~

G....

....

..a

~

...

.0

Cl)

\.:_

..

s.

0

C+

~

)(

t!

(' i l

c ) '/

' I l, j oft

.

'

) @

"

u" ~)

I?

o I

' )

1" ~~

..

•I

'. ~

; ~.~. q I

0 (_~)

.. J

1

..

~ Q 0 0 0 ~ 1 .. "' 1

"''~ 0 6

..

J .

..

0

'l

""•'.

' )

( . •

" 1

" '(

' /

I _•

I I

"

~~ _,;;~

t·

"

"'

(~ j 0 ; )

'{4 ~ ( I

;)4 ; (. (

,' ~ ~~

..

0 " 0

r1. "l 0 'I

2

10

I G.

2..

'!>'1

AI'\

V&A~US

MOLE

RATIO

OJ:

12.:

Sbl).btpy

{upper

a.w,c.)

AND

b•p)'

:As

1

₃

(lo~c.r

cur,e)

8

OCClll'!'

i

t;o

~­

!;

vm:i

ion ao ( 1,) (

c.

ne (

v

tton v1ae::1

ion

-(

i

1

1i rJ tt io:nic

e

tH' ava.il

I

!i f3

om

as

1.

iu t

c

···~

on

, to

't lH3

c

(

.

Gl.

?1

c

.t

accord with those to be

oxpecl;cd

on ionB c:a.:n bo

,, \

,, J

I

t e h

e I I

en ex•

on

(

t.o

!'tH1tl t t

to

i:l.t

01

p

As

-1..0

5

0.,6

I ion i::J

on

c

cottlmo.n

(

I I

i ) ';l

"··<> .J

0 1" 0,6 ts is i to

t.

() b

(

I

9

0.,6

Ett

t :l.G

on

v:i. ti.t :to

ltnl

On tl1c other

ll

n ure u litLl 1

tfbilit;;,r c;'!lr:lr.'n.ettn•i :J.rm i; X' ;1] lli I

t

lrtt Chi.

COVC::t1

(

'llt .. O

0

'

.. :toni .t. ;, lHtt

ion t

oi' thn 11 tc:r•

ace ore! it ' t

OW

ionin.D.tion nt t 1 .'. 1.1

,., ,, I' o:i' (fllCl i

co val

tol

( t'

to

t

o-l.

Iorw of

~~

1)

+

A 1\

1

tlJ (; 0 tlG t

( )

OJ'

i cncu:

e 1i E:rn

Int ion OI'

r ace o:r·

ct

t ou

t!mn 'b:l

l

i :i p to

ic iti

tr1e

on the

tG

om

D.!l<'J.

s

nn.o

')'

al r;o ho eovn.l in

u.:r.• o:e n t ( )

have bcc:n. 1

;l i vo 9

OIJ.t t

OV!

ed lone

8

..

It :tn

!'

1 b 1 1 1)

9 .. 99

(s)

9 ..

(m) B ..

(s)

6 .. 83 ( VJ) 7,.83 ( ) 7 .. (e)

5 .. (e) 6 .. 71 )

6 ..

(w)

)f., 95 ( ) 6.11 ( Vl) ~5 (

)

(m) r;,. (w)

5.Jt.7

( )

( ) ::; "Olt. (m.) J! ..

(s)

('w) ( ) 1 r:; (m)

2.;7f3 ( ) 1! ... 15 ) ( )

"

) 91 ) 1 (VI )

c~ 3 (m) ( ) ,., r .•

11 .•.• J p

1 o,t~.o (s) g 0? (s) 8 ( ~1)

[) (m)

₇

_(m)

₇

_(m)

7

(m) r u (m)

6

(m)

(m)

5 .. 0G

( \'l) '.).,10 (lN)

G .. o5

)

_T'>

(m) ( )

(w) (m) CJ1 (m)

I r"

4 .. ) ( ·o) 0)~ ( f3) ( EJ)

01 (rn) ,-l _(m)

;~

.. 70

( Ul)

c.,($

L!-7 ( T'l '"l ' ) (w) ~J. _{.. )} ( v!)

"' ... I t_ ...

1ft. (m) •)

b b

n

h

8"71 (m) 8 .. (s)

a.

( f:J)

7 .. 97 ( )

_7Q

(rn)

_{7 ..}

(m)

G,

(s) r o,. ) 6 )

5" (w)

5.

(ill) '5"' 1 !! ( El)

!~"" (

,,

)

\ b,J 9.3 (li.l) (m)

!· ( • t:J' ,. ) 7•') (C. ) )

'7

) ( s) ( ) ( c•) _{\ •J}

( ':1) t~) o·;< _(HI)

(;~uCJl! \

(,_. .:J .. ) _J

1!0 ( iil) ' ) ( ) f ) ( )

('_,., t ~ 0

1 (rn) :23 (m)

.,

( m.)

47

r:Jl1 i

QF1I'!' in n 0

io:rtf'l, an

/1 c::r.• collect on n :fililor

VHCU'llm,.

:ted

to O,l'nnn1

I I iJ :lud

'ti

Gal 1

1~

i tn.t. 1 1· _{·' ov.: It,} \JtHJ

1 t~~; ~v

on e:x:.po n t~o tho

foP 0_..

I

'5;

an or

t s was

cului~ fm.>

o

10n

on1

A cm1a1:; 1 (~,

' 9

rr

7 -;~. (''1 '17 7"' . 9 .. ~) , ' ~ c. "' •

., 5; H

:tll

tr V'ft't%.1.

i.lt

hot b<:1nze:ne

Ll ite

en, ..

F'ound!

o:nc

( '!·' ", "'l • . ') )" ~.: ' , • if- ,

,.,l.l

(]

no

t

tion:J BrntJ.

1

t. ()

.

..

,

t

oi

io-(

i l

tl l '

11.1

s: c~

is

0,16,.1; 1,1~3;

tion) i

ai:ano ic rnoi stu.ro ..

01' 0 9

1 I' VJCI'O

n,1 1>9; n,1 ..

in YJ.?ln 1 iee

~: c1,16~1; o:~1~1;

.}

ion

ect

as

ox· ion

i ;

(

,ooo)

.

2" 0 , ) 1 tt. ; I f , ;) o ·1 ;

2 . [): • ' > . . t ,

1s

is: 0 tocl

('.·!

'

'

o;

d. 1' V!

..

d1:i.octor:Jt1b !ill 6 1:11 achL.

A solution

wat3 in

vacumn

1

c l was

i l l on to a I"')

ile

i-1 J<!Jp., 1'7l .. t, .. 0

to

ton occu.rr

f:)()

tter•n

was of'

v

OI' \!fli'O

r Gf;

;2

-sO ,~p ·ri

/'., -~)

•)

) 1:'

1 1

') ) _~~

'~-ion of'

( :r• ion)

1.7.

l~

L 1

)

0 1,.) ) _1.)

c

)

1

ion

1

l+

>

!-·>

) 1,1. :.~

n

1 ., -·· ) n _l

' )

,) c

by a ion of'

Ir10r

;n•ooni

100 ml of s

t.o

cono., 8.C

st;

(lit. 11 ) ..

by 1 ).~J,.

ml ilOl in a

\"Jl th an i

j"c ac:Ut

;:~

l"1Cl8

1lt

_J:'·~)

.l',ftE~r t~t

vms and t cool

th.e 0 waa

cvolnt:ton waB

to remove alcohol,

the

18 6

.3 1 8

ter:i,

lot't

:r·

}~ l;:~

~

i _{') ,_}

ion ar3

Vln.n

It was in a COIJC,.

ethanol e (1:1) 100

r• ( 80 rnl co:nc~ 1tydx•oohl c acld. lui.;

·1 00 ml vd ) .. !\ ft ex• oool ocip:ttat

th cone,. oh tc 11c

ion

to

t.io:n.

d.i

6

1 1 l.

IJ tio:tl

" .'~.f~'iJOIJ fil n

VJt--lS

:tc acid ... "'~HtlS

9 fJ VIa YJ vor•y

t 11

or

100 ml

foP

t:l 1 1

to

i

·j

10 (:._; o· in !!G

OI' ac • 0

stannous

o 1loric aci~ was

57

11 sol

was

s warJ filtr

dr•y. isntion

as

).

On cool Elolution l)y eli

ibinic~ ac e

OJ.'

ichlo:e tt

solution this in. diluto ac lee

ol1l

d. V/(11:'0

f'ilt sic OI', m., p,.

(1

EtS GCI'

Phenylmagnesiurn bromide was

ml

over 2)0 minut. e~:J. e 1ras

irred

ismu

.3

1 from

benzene

6

T of b

ar

t

Uo.1 ()

:1 V:it::I.EH3

2 no

"

0 _{" _)} 7. 0.1 _Lt.

')Q l)ipy

l"'!._

1 r)

" <~

;~. "1:; V)0

c ..

bO

Hio

t

0 0 }-(.

t

to c

to

,

ThiB ti v:t of.'

L1.;,~~

.. g ohrn- 1

-1

e

in

nitrobenzene~

ated as a

2:1

olyte, (

s beh~cl.viour· lals

t

co

idyl 1jO _{th:ts ro}

mm.•e clo a clilicon t

or 1 ~J

i

]) _{cl with}

jJlyl t

I' ri

iHOJ.'El one 1

All 080 s

1

re

l::Jond.s more

"h,·y· .. .., alHJ

"~·

ut o " 0 '" Jl\..

1°

1

~B

o

1

onrJu c L i s t;

0f:)

to

to a ent than.

)+ _{( e}

f e iott :i.s

that mol

Ol'

wao se

e

I

)+

9 (Me

can B66!1

V it is

It is low c i ti

oe

b

o:e s r:1

n.on-with. ·the

can

or

only

results. lt was fov

()

co :it ion

, complexes

(PdCl., t )Cl •Ner·e

50

OI'

s as an

Ir'onii 9

Ill ionB

nat tvm r:Jo to for•m ()

whi nn1st

e o:nly one t

r~ntil an

a

Oox11 " ion

t1w

z

atom to be

coord.inat to of

is

to

involved., t exes are rwt r::o

st :f'or a tr

e mol I l l

anae wan 2., smn :l.i tin

(~2 .. 1~0 di::3ta:n.ao

1.. ( o t:ln

le

c

3 found thai1

chelate ~:v:tth silicon

t

no int ion

idyl

nncoord.i:na

t

fnncti as a b er

other• :idyl J •

Ge Hl

no

( e

1

1,,

<·

(}

Cl

1

9

or ide

t

G

ion

"

(a)

t

s so

(~

'-" lt

~h- ?

2 no

(M )2"

'15" 3

(a)

t

terpy

t

(lic~hlor·

two

(n.

c

)

t

1 1

~ Q '

o:r

t

t

are irwoluble Ul()tltJ

"'' 0

:lve 6clSC':1

Por•

EHltnC r•eason,

tt~~L the

i<.'iyl ~vith dimethylt

one

as al

In ni trobe:nzene th<E~;y~

s

( t case o:f:'

ation of'

t

ief1 of' 17 ~ 9 1

c t of

t

nhlor

in

idyl,

i vi ti<EHl

ar'e

CElSE~

sod.iurn

(

..

.. 13

t)

~ . ( "

"

0.. J.

o.

l

().,

"

1 ..

"'

7.,'

I } (I ~)

"

m (

orbatrary

unat.s)

VERSU~

MOLE.

R"TI

0

terpy :

Mt.

1

5,

C.l1

0·15'

O·f

0·'1S

lol

0·5

1·0

'"5'

3 one Jnolo

one onrves ;11 so :r•

occu.r et.l

it

ion

) t ₊

3

2 + t ~-···

ex

t

o l~in

( ons,

only

ion

cro.

occl1l'.'l"' enc e

R

s d

or

to

s of 1:1

t

or

are

yel

e :i.n

t

s

( e II) that the

lend

ictyl icatcs rli'f:J !DOl'El I'

anccs

oat; ion. t

t

(S 80

•t

0 t

5

0

cUmethyl tin c

2" 'bipy.

T III lit"lts the

is ava:il ocline

, but it 1 doubtless follow t

tin tetrahromi<le in

Tho dipole Cl

91 81

76

are tabulated

Dipole

H 1 1 Ill

03

Tiit _LtJt~

}iJt 3Pb01 I~.

s of a

s

s

in

of

1~=:2 1~n~

IV ~) "~ I :J e

5

30

1 lh 2•1

I 51 '10

t

t

corr

( cal/mole)

('i

lq L17

,;}

e,,

n

rJ

G. 21

l,j

'11

eme

moments,

been

OCCUI' I' e.xes

t

atom to

s

cliha.l

, as

so

is

Howeve:r•,

e

7lt.

to

t

is i

or

ies

'12...

i it3

(')

by

73

by the

1

H. hyCJ.r

cr•yot s on a B

i

u thEH'lE} pr to the

8.fi m

2

be.m:~ene Bolut ion c

oro-'if ~1 s ( J • .. l

t

• 1~.1

Ortlcul

Us

Calculated. fo:t•

c

_{1 1},1\!

2Bni2:

q. -· '~

c

11

2.5.

a; n,

:B'ound: 0,26~1;

H,2.7; N,4.

solutions of methyltin triiodide bipyrid;rl v'!ere

it ion),

stse Calculated i'Ol'

c

1.1

u

11H

Th.is

Gt

colourless ne

c

oleum

6.-,r:·O

El, m .. p. ~,.J ,

at

:ic nol vent o

( .r::o·

) -

70°)

ttS

snJnH mcrnnm• as the hi);>yridyl

i Vf.i.t i VCH3

as the solvent since

insolu.1)1c this solvent, and h

using it~ All the

nitrobenzene. b(~ X' 1iGed fx•om

141

ipitated as a

th

o.s

II lfl"

:p "'

1

OL~

0

~

1

i £:1 :

c

~::ll cu t

(!) . •

J,

dimethylt

, m .. p., 11.3

of t

fo:r> C

"1

idyl vex•c:n:w dimet:tJ.;vlt

H. ~ 1 1

"

31

1 ht'l.l

petroleurn

t d

p 1 G

f! •

·''

t

idyl

all

i

is

n

_c1

N ~6~

1~1 _{0 8;}

_{95 ..}

the

cream l'!Oloured sol was oht

s·

.

C' , I f'o:r• c1 _{1. ' l}

c:.

N,5.,0; _'37.,

I•'

_{0 '27.}

.

ff~2e9; H "Lf ... 6;

'

t

ol f?Urn

ye1

ion of'

at

Eiolutio:n (F' lt.)

in

powcler ..

f ... ·.! ,cJ,. r:

6

:>

o1c:mrn

I

t

eo

a

1 1

tnt

0_17H1

ecip

1} :

l·

11

₃₁

0

\ j :11 ·t· ;

n,

IH

dibromide, a

~

..

the

1

1

[:}.. s [J

··.; t 1' o·r1· )

n

cJ·· n<.l., ''· c' J.,

>.JJ. J • . · <> A - l

ll tn

ion. 11.al icle ['JXtd 1

iniethyl tin oleum

.not

t

to

ions (

b

lt

::ts~

c

ox ib

!fl., p 0 186

0

~!'his

o

₅₁

Ir

₁

+

₁

r·T

low soln.bility of the

di-on

idyl

or four molnr excess h d

1lce

J:l' te

s Cl culat

for

c

₁ 1 '):

n

9 LJll.,?;

n ,

o;

'"·

V!hite

d. eec>rnpo

s:

C cul C r;•)I18

(;,,w L~ J 2

Lh 1;

c~

..

5;

H~ 1;

_{7 .}

F

p

not

s

p

is: () ·j,;

5

6·

,

..

,

l''ouncl: C ~ l~.3 .. L1.;

El

)

1

il;v

and terpyr'idyl

slowly

0

for• ( ' l r

"'')7' ,

..

9 21.

r) a

E.,' '50

3;

c;'

~ 21 G

0

, m.p. 180 ;

ic:lyl

3 .. 6

oxes

D.n colourless

On standing this complex separated from othanol as

.'\na.lys:i :3! Gal cul at c:d

Pound:

Ho solid cornpounds wcr•e :f:'or·med l)etwoen ctiphenylger•manium

diehloricle and diiodide with eitb.er 1)ipyrtdy1 or tc~rpyi'idyl

under• the r:n.une r•eaction t.iorw aD produce complexes with orgarwtin D-Ild or·ganolead halides,

'J:rw

ini:;er•action between germaniurn tetx•aiodide and

bi-pyridyl \iiJas exawi:n.ed. i:n. a dr;y--box. l\ three molax• excess of 1:>ipyrldyl in socliu.J.n-dr•iecl ben~:wne wss ~:uided to gern:u-:,1nimn

t;etraimlide in thcJ ss.rne sol vent .. r•esu.lt ing red-brovm

solid was fiJ:tm ... ed off a:nd •?lashed with 'benzene. This conrpou.nd

minute::; osed to t;he a

1,G ei 11 :

t.,l 'l"

'bl

I\

1.1

tr eel Ylith.

r wa.s

It VJD.S

i t

for~ t •1 ₁

"

OW

>

e 1

HI

+

.3

ton een

nos

't111I'

over•

c

11 hi

so

ac

f i l {>rat

1on

i VJil.S

It

ca.t

of' cone., lc ac

benzene~

l

vo.cumn~ eal ... l

T with

2 es 1Ue:t• e

( i l l

on a tJ1e

oool was

by

ess

filter Q

ni tromethane

i59

yj.elc1ed colourle-:;ss

(lito

159 70-71°),

t

or

t

of

freshly di illed hydriodic rrlte t

filt off on a sr1 cruc::!.ble

1:18 po11

r crystals frorn

i orw m.,p

t

)

O:n

alli

7() 0"

s, Jn.p., 7

to

as

1()0 on

( L1

t

th.o

to

e

to cool,

er ( 1_1(J.-70°)

, mGp&

42° (lit 161

A sin11 :ion b t

t

I" 01

;) _L.>

•1:i.

t

1

i

)

r;ome

t

)

ion

lilD.nner f'ror11 50 no

tin.

t

le

f'o11 (~

ill

e that

bulk

i cr:nae

over·

th.is o tetr•

t:h.is

t distill

/\ 0

t

\VaEt

the r

r p ( )

£3 of' di

m .. p., 1 )

.

D:trnethyltin 1Ii

tr with ;just suff1c ()

s p

t

to

1 D

ers li

1

te

~l1_{.h:ls was}

i

.!. b

on 11 fil

to

"

s,

m ..

_•

t

El

1 , as a

ith cone.,

on a on cdl;y· 1

OU!Il (

(Ll.t 1 75~77°)

( (1 I' 1 c i l molten

1~il ter

)

t 1 f7 ()0

0 _) '

r'OO!U

t

t T' 0 L) assiurn

cohnl was

hours

A:Cter•

eum

i

ion

ound so1id

s

ter'

tri dilute

~

s H

( )

,,

I

ee

ene

e~ 500 ml

20 g of stannous assitun of'

er bath~

was fi.It. off' t t3

'\!! it:h aome

(1

'b:t• ornid.e f'

all

181 E oi' 1 I ee

te

400 8oxh1ot

to

t

(lit.

169

).

10 s of

t con~

Et littlo

di.hal _"

D ssolvec1

£1 of tric 8 ion of

ctilute oric an ocipit ed

s was same ma:n:nel" ~:w

f::~olu.t

ion. n A

;yellow

es as 88 e .. nlli om

C ondu.ct i vi ty

ent

"

by

K is the

solut

1

pot

as ide s fl

• o±o

1°

C(71l const

fl.t various intervaln, but

u.nreact

r· atively ic

in this to

ctivities wei'e

x•elationshipA

tivity (

1

~301 vate 8

(

us

1

1 '"'i"1 u.l. )

1

ific

of

ibr•Ftt

to

it _:ts '

It 1:!.

) 172 ' !>

e limit conducti ty of a 1

elE)ctrolytos this

1 vi ty rnetc::tsur s C)n the bismuth halid.e c se r3olub111

t

s in nitrobenzene were very low, WEJre also made

dirnethyl:t:'or•mrunide; but 1 oth.er rneasur

nitrobenzene. Limit molar oonfutctivitiea of strong

1-1 ectrolytes usually fall the

A

0::::25-35 in

17""

nitrobenzene ::>,

an ov·em

mol

mo:t

by m.easur

A solutio:n th.e 1

solution

at 1

climethylforma.mide 11 5

~

c ant

to c~ool The

r::tt lm.th at

the exes

to t ~ 1 s not r1eces

vvere ti t:t'ation

b

ten

was att to cell by means of a

joint.. 'l'he measur ivity Wl'lS

di:tut.ion by :m:al t by th.e

_'

₍

solution,

plot

tea

mole io

in th.e !'SBUl t curve indio es

point .. 1 constant of'

(·1) Ni

176

illit:nns). ·was

cm.>e

rise

em --1

( Ff1

(C))

\ ~.

and

1

e.,

1t

WHB

J-th tJ

B.

~ (1!' st;

4/\) this 1,h/(:18

N yr'

' ,_ '

D

er•r in,n;t on 177 .. by

ill

if'

the t e

(~

f'urtr1.er

Wl'l.S

It wn::3

ic i

t

by th.e

(,y ,,

or

wns

call

mol

to lems

if

;('

1

s

Y :ts

solution

it

not 8

-7

·1

ohrn-... 1

em ..

t

ill to

-1 -1

ern "

Carbon, and nit:t• clet tions ·were

car I' Ol.:l:t the icroanalytical atory of the

Uni-varsity of

Ot

by Dr.

A. D.

Kj to

" .. )

solution was titrated

w

ions~

as :t>ecornmendect by Vogcl 1

78,

th

e ium

FP.his ac~

e solution

silver nitr e was

chlm: In the case of

ni i;robenzone

titration

on approximately 0.2 el:l of bipyr:tdyl

solution o.meter~ ..

over C<3.1Citlll1 chlor•ia.e ..

phot were3 obt

a

Phil

11,48

em

er ct::unera :f'ilt

!':! :f' i.l t ~:rr"' • I

_'

t

V1El!1₀

\'ire:rae

f 'GO (,

1 (:' _·' elze{il

al"' ex.e the

I:n i srn.,

I' ive

A Bt VL"iCUUJtl 1 Wt:H::l f.'o:t>

en:

us

pu:t• yolati1e b;y i a series

r s

io:n 1 \VaS s

was

t.

s

1. I il nor~ (..) 0' a:n.d G n~ Oht.1li1.. ~~ I'C:V • ~ ? (1 )

.

·~)

f,.Q _~ (1~)511).

"Z _{,J .. I ( 1}

) "

:;.

,

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lj . ., L l<b. f':' _{( 1}

) G

'

2?

5., lison ~

s ..

Doc.

,

1 !) , (1 ) 0

6o

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Lc~:t ttiE-::, ,T. :Joe _?

,

(1

).

7~ if,s, ;r. Q • 1 ( 1

).

8..,

,

_? ,T,

"

c;·he:~rn., ~

J.9

1 ( 19

" ? 1 ~) 21.t. ( 1 .) 7)

.

11"

c

1

1 ).~ .• 88

H l.j:l :tl T c.

'

9 "

.

'

/

ex• ~ ,J. C' ,J

"

_'

19

( 19 )

.

" J<

x•t

•

,

1 ) $

( ' {'i~

) ®

l ) _•

,

9

.. ~-1 ("J·"'·· 1()f)'·1 (·1li )' ..

, ,J $

c

1em, ..., , . J ,

3

,,

..

40 ..

os, d ompt" rend., ~

rD.U£l

ios, ,J. Arne:r.• .. Onyozchuk,

son, ,T .. G

g i l l

' 51iJ.; ( 1 ~itt.O ) "

F'ia1 ster }ll

EJ t E~l1

onl1e

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'

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1

on Davies, C

,)'., (~ _J

'';'' ;~ l

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,T

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( 19 ) •

( 19

)

&

1013~~ (1960)

Soc.,~ 1 ( 1

(.i 0 \,)

(i

$ 1

l z7J ( 1 C

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)

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(1 )

, 97 (1911)&

" 9 11!.~1 (19 )~

' 82 ( 1

)

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1~6 ..

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50 ..

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on an.d.

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and :1

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J.

Chern.

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..

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..

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L~~w ( 19 )o

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Doc.,,

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..

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1 _• Oo~:tton, :r. C

'1 -1 01! .•

HJ:J~ 9 7.,. :.UJ.OX' •

1

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1

1 09~

11 Pani, a .. J

1 1 1 $

u

1120 p

1 1

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115. !'hill fJ , ,.T.,

..

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(1~J ),

) "

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1 p :\,

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1

HtB~ Ghall

1

15L

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r-15 15l+. 1553

1

157$

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105

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' 1700 ( 19 ) G

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$ i3oc, t , 1 ive

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