Syntheses and vibrational spectra of xenon(VI) fluorogallate, xenon(VI) fluoroaluminate and xenon(VI) fluoroindate

Journal of Fluorine Chemistry, 11 (1978) 5 19-526 0 Elsevier Sequoia S.A., Lausanne - Printed in the Netherlands Received:

October

SYNTHESES

15, 1977

AND

VIBRATIONAL

FLUOROGALLATE, XENONfVI)

SPECTRA

XENON(VI)

OF XENONfVI)

FLUOROALUMm=

FLUOROINDATE

B. iEMVA, J.Stefan

519

S. MILICEV*and Institute

University

of

J. SLIVNIK”

and *Faculty

Ljubljana,

for

Natural

Sciences and Technology,

61000

Ljubljana,

Yugoslavia

difluoride

at 14O’C

does not react with

SUMMARY Liquid and indium

xenon

trifluorides,

the reactions

between

neither

the corresponding

N2HeGaF5

and N2H51nF4)

N2HGGaF5

and N2HglnF4

yielding

only

at room XeFe

does liquid

and XeF2

temperature

. GaF3 and xenon(VI]

Spectroscopic

XeF2

at 60°C while

fluoroindate(lll)

polymeric

gallium,

at 60°C.

Therefore

fluorometalates (at 25’C

(N2HeAIFg,

anions of the type

with

yielding

contaminated

these compounds

NpHeAIF5,

in the case of indium]

the reaction

in the case of indium]

evidence suggests that

squashed between

hydrazinium

trifluorides,

(at - 25’C

aluminium,

hexafluoride

and XeFe were carried out.

react with

the corresponding

xenon

with

XeFe

XeF6

proceeds

. 2AIF3,

indium

trifluoride.

are salts of the XeFg cation

(M2F7]z-

or (MF,]z-.

INTRODUCTION

Systematic xenon

studies of the reactions

difluoride

[l-3]

elements of the third and xenon(Vl] aluminium,

gallium,

materials

for

hexafluoride

and indium

the reaction

fluoride,

RESULTS

AND

Preparation with

with

xenon

transition

[4-81

that

xenon

extended

table, where only The study

hydrazinium

hydrazinium hexafluoride

the reaction

metal fluorides

were recently

were so far known. because their

[12]

in situ during

to xenon(Vl)

hydrogen

trifluorides

[lo]

it was found

formed

between

hexafluoride

main group of the periodic

fluoroborates

[ll] . Namely, fluoride

or xenon

xenonfll]

was limited

fluorometalates

fluorometalates

fluorometalates.

Hydrazine

and lower xenon

fluorides

reacts with

to the [8] to

are known

are good starting

because the corresponding

immediately

and

metal

excess xenon

is being oxidized

and nitrogen,

are formed.

DISCUSSION of the complexes

by treating

a larger excess of liquid

xenon

aluminium, difluoride

gallium,

and indium

or xenon

hexafluoride

was

520 unsuccessful.

Therefore

hydrazinium

fluorometalates

were

taken

instead

of binary

fluorides. Using action the

with

hydrazinium xenon

case in all similar

N2HgMF5 n >

fluorometalates

difluoride,

of aluminium,

no xenon( II)

systems

studied

+ nXeFq

6s

+ nXeFp

s

up to

MF3

gallium

fluorometalates

and

could

indium

for

be obtained,

re-

as was

now.

+ N2

+ 6HF

+ 2Xe

+ (n-2)XeF,

10

M = Al, Ga N2H5 lnF4 n> Xenon fluoride, molecular

form

to get pure

the

hexafluoride,

reacts

should

with

xenon(Vl)

amount

oxidation

of of

trifluoride

+ Ng

+ 5HF

xenon

not

At

fluorometalate

hexafluoride.

room

hydrazinium

and the prevent

Therefore

slow

of

final

the

product

reactions

fast

developed

between

in

In order

During

reaction

di-

in situ

trifluorides

contact

proceeds

xenon

fluorometalate. with

heat

than

obtained

as possible.

good

the

reaction

.2AIF,

XeFg

shown

temperature

It is stable

hexafluoride.

The

by

which

reaction by

molecular

is only

the

corre-

as follows:

+ Np + HF

pattern.

was followed-

which

gives the

pattern

of

product

N2H6GaF5

2AIF3

+ XeF4

XeF2

and

mole does

up to

+ Xe

+ excess

ratio

Xe

show

XeFg

solid with

15O’C

where

decomposition

The

carefully

not

25’C -----+

+ nXeFg

is a white

vacuum of thermal

diffraction

analysis

the

XeFs

in dynamic

end product

its X-ray

mass balance

purity

: Al : any

. GaF3

of

XeFg

the

:2 :

F = 1

. 2AIF3

12.

+ HF XeF2

vapour

The

trifluoride

as

and

X-ray

by

by chemical

diffraction

of AIF3.

+ XeF4 and

loose xenon

was checked

experiment,

lines characteristic

+ N,

negligible

it begins to

is aluminium XeFg

throughout

little

Xe

+ + excess XeFe

10

At pressure.

room It

begins to composition shown

ion donor

10

pressure.

n >

+ (n-2)XeFq

trifluorides

contaminated

gases (Nq, Xe, HF)

a

fluoride

indium

little n >

+ 2Xe

at as low a temperature

However,

+ nXeFg

and

of corresponding

slowly

evolved

trifluoride.

N2HsAIF5

is a stronger gallium,

fluorometalates

out

hydrazinium

and

which

aluminium,

by oxidation

be carried

sponding

lnFg

10

by

temperature

is thermally

loose xenon

at

diffraction

GaF,

is a white

less stable

hexafluoride

was complete its X-ray

XeFg

a little

150°C,

than

in dynamic with

pattern.

the

vacuum

gallium

The

solid with aluminium

purity

already

trifluoride of XeF6

negligible

vapour

compound

and

it

at

The

de-

130°C.

as the

final

product

as

. GaF3

was checked

by

523 mass balance and chemical The X-ray

diffraction

gives the mole ratio Xe : Ga : F = 1 : 1 : 9. . GaF3 does not show any lines of gallium tri-

analysis which

pattern

of XeFe

fluoride. N2H51nF4

+ nXeFs

s,

InF3 + mXeFe .InFg

t

N,

f

HF +

XeF, n >

+ XeF2 + Xe + excess XeFe

10 The reaction

hexafluoride reaction

between

proceeds already

is thermally

was impossible

unstable

hydraziniumtlt) below

to remove side reaction

hexafluoride

without

most of the xenon(VI)

indate(lll)

always present.

The vibrational TABLE

hexafluoride

products

(like

xenon(Vl)

fluoroindate

was indium

This was proven

formed

below

XeFs I.R.

spectra (cm-‘)

fluoroindate.

with

by the X-ray

of XeFG .2AIF3

After

some xenon(Vl) diffraction

and XeFe .GaF3

XeFe Ft.

. GaF3

of the

pattern.

(Table

1) were assigned

Assignment

w-m w-m m sh

I

v (AI-F)

-.I

650 sh

654(100)

*1 Y (AI-F)

634 vs,br

sh s,br s,br sh

453 w 430 w

623 (24) 591 (92)

619 vs

585 (27)

579 559 517 486

485 454

621 (28) 598 (60)

*7 *2

580 (50) 517 490

(8) (2)

Y (M-F)’

(1) (4) 420 m

436 414

(8) (4)

417 395

(3) (2)

360

(7)

364

(8)

328

(1)

293

(5)

282

(6)

225 (
w w-m m w

it

fluoro-

R.

I.R.

the

more than 15 hours

The bulk

and XeFe .GaF3

. 2AIF3

654(100)

584 551 521 494

during

O°C. Therefore,

XeF2, XeF4) and excess xenon

was decomposed.

trifluoride

spectra of XeF, . 2AIF,

and excess xenon

fluoroindate

1

Vibrational

1101 905 744 664

also decomposing

was left behind

Xenon(VI)

and looses xenon

of pumping sample which

tetrafluoroindate(llI)

-25°C.

230 (
*3

*I3

I

"9

XeFi

522 in the

usual way

complexes

by comparison.

[13,14,15],

. HfF4 [ 161

XeFe

all the

spectra

some of the

of the

were

ion

any

retaining

differences

significant

octahedra

splittings

and

available

[ 141,

cations

result

in this

to govern

complexes

which

bridged

the

between.

complexes the

region

symmetry

of the unperturbed

should

essentially

effects

seem to

in the

Consequently, with the

deformation

less intense found from of

The

band

intense

part;

the

and

modes

should

cation (XeFg

structure

of

in all the

. HfF4

XeFe

band

investi-

[ 161)

without

in the

degenerate

deformation

site symmetry

of

XeFL

bridges,

XeFL

new

the

a type

with

anions,

is found

and only

[ 191,

follows

the

and

is reduced

the

mean

more

complexes

of y2 and

(590 f

2,5

to

in C,,

of the cation

and correlation

[13,14]

symmetry.

its subgroups placed

be shared. intense, should

pretty

If,

of IQ.

Interaction

Therefore

Y, which

gain the

C,

of or

is usually

has been always

in intensity same

well,

because

Czv(ev),

and v4, which

v4 is almost

cm-‘]

data

lower

as closely

intensity

be relatively

published

basis of

or even as a shoulder,

arithmetic

investigated

the

and

forms

or fluorine

of the

ZrF,

split. Therefore,

same representation

occur

V~ should

as a weak vz.

XeFe anionic

on the

symmetry

the

should

than

of the

assignment

C,,

take

them

[8],

spectrum

understandable

the

y4 will

c, (O”L between

FeF3

is very

the

part

instance

where

be negligible.

(M2F7]E‘

monomeric

the

of

spectra,

to

and

of XeF+5 spectrum

lattices, with

Absence

anionic

deformation

crystal deviations,

contacts

Raman

forces

case of

spectra

known

in different

effects

in

presenting

standard

crystals.

in

only

lesser influence. the

the differences

intermolecular in the

XeFg are

determine be of

the

(MF,]E-

bonds; see for

Raman

within

of field

here,

to

and

appearing

Raman

now

bridging

rules in IR and

consequent

mode

stretching

published we are

shows, within

packing

structure The

XeFe

polymerization

the

Fluorine

site and

bands

as according

cation

the

same type

(including

The

hexafluoride

XeFe .ZrF4

bands appearing

spectra

understand,

[17,18].

packing

fluorine

The

between

Raman

are reported

case in stresses and

[ 131).

anion.

XeFg

of

octahedral

crystal

by stronger

complex

selection

influence

somewhere

IAuF;

to

of the

the

and the

xenon

[8],

in size, shape or coordination

seem only

modify

is deformed fXe2Ff,

the

symmetry

indicate

placed only

easy to

C,,

fluorine

which

not

of

.FeF3

also considered.

differences

anions,

spectra

XeFe

- cation,

and the

differences

preservation

In the polymeric

corresponding

are

monomeric

were

XeFg

noteworthy

published

complexes

anions

in its complexes

its approximate

anionic

regard

to the

are some

with

of the

assigned to the

spectra

The

Besides the

spectra

polymeric

XeF5 ’

(Fig. I].

gated

with

There

structures hardly

the

and

in the

move

whole

away

series

[16].

under

is hidden ln C4” degenerate Y, should be split, but it seems that a component the intense bands in the vicinity. It is clearly split in XeFLMFg (M = Zr, Hf)

[161.

v,

is the

is in accord molecules. modes

most

with Because

the of

intense

band

observations its small

in the of

infrared

Begun

intensity,

of ~8 and vg are split as expected.

in all the

et al. [20]

vS is difficult

for to

studied

complexes,

a series of observe.

The

square

which pyramida

degenerate

523

XeF,

ZAIF,

623

L____.I._~_L___~_

7oc

__ 1. .~.____

600

500

..I________I~~__L

400

300

__

200

100

598

I 580 I

XeF,

GoF,

621 I

J1

u _._I

700

__~__

600

I

.~~_

500

~___._~

100 Roman

Fig. 1.

-1

shift

Raman spectra of XeF6.2AIF3

I

~.__

300 (cm’) and XeFs .GaF3

__1L

200

100

524 There are only spectra with in comparison XeFl

with

ion (660

anionic

a few things which

certainity.

Fluorides

the XeF5+ ion. Strong

-- 580 cm-‘]

bands. Moreover,

400 cm-‘.

can be said about

of the investigated

Therefore,

in both

absorptions

in the stretching

part of the

Raman scatterers region of the

Raman and IR, may obscure some of the

the infrared

it is difficult

the anionic

elements are poor

spectra end, because of window

to obtain

unequivocal

proofs

material,

at

for the polymerization

we. For the aluminium ometry

double

the aluminium

should

on the basis of stoichi-

broad and strong absorption

shows very

which

might

be the consequence bond

very weak bands are associated with bands assigned to Ga-F complex

terminal

an anionic

AI-F

polymer

The infrared with

of polymeric

stretchings

spectrum multiple

structure

of

peaks

[21]

and

122,231. In the Raman just two

vibrations.

stretching

is contaminated

Nevertheless, its Raman spectrum between

we expect

complex

be assigned to AI-F

lndium

complexes,

or sheets of (GaF,)E-.

(750 - 500 cm-‘] which

and gallium

sheets of (AIzF7)t-

The

gallium

complex

shows

vibrations.

by an unknown

shows the characteristic

quantity

of indium

features

of XeFl

trifluoride. squashed

structure.

EXPERIMENTAL General apparatus Reactions

and techniques were carried

vessels with

Teflon

compounds

used or prepared

Therefore,

all transfer

in argon arc welded

under vacuum

nickel

valves and appropriate

during

this study apparatus.

radiation

Radiation

2 mm o.d. quartz Infrared

was used for

gas phase work.

silver chloride X-ray

an ENRAF powdered under

photographs

Holland)

or by distilof

a Monel-

1401 double Radiation

Art

monochromator.

using Perkin-Elmer nickel

cell with

samples were loaded

521 and Zeiss UR-20

AgCl windows

were later sandwiched were obtained

using graphite

As

laser and the 6471 A

box. (A.D. McKay, by dusting

in a leak tight

by the Debye-Scherer

monochromatized

samples were sealed in 0.5 mm thin

Raman spectra.

with

Spectra of the solids were obtained

plates which

powder (Delft,

length

box

line was constructed

laser were used. Powdered

spectra were recorded A 10 cm path

in a dry

and equipped

using a Spex

tubes in the dry

spectrometers. onto

Kr+

of the

range.

the 5145 A line of a Coherent

line of a Coherent into

either

The vacuum

lines and connectors,

gauge for the 0 - 760 torr

pressure and weighing The majority

are sensitive even to traces of water.

was carried out

in well dried

Raman spectra were obtained exciting

nickel

valves (rated to 100 atm).

of materials

lation

Helicoid

out

packed nickel

walled

quartz

CuK,

brass holder. method

radiation.

capillaries

Inc.]

samples on

Finely

as described

525 Reagents

Hydrazinium(2+] zinium(l+]

pentafluoroaluminate(lII],

tetrafluoroindate(ll

Trifluorides

of aluminium,

the corresponding hydrazinium temperature. diffraction

The intentity

pentafluorogallate(lll]

I) were prepared as described elsewhere

gallium and indium were simply prepared by reacting

fluorometalate

with fluorine under pressure at room

and the purity of the products was checked by X-ray

and by chemical analysis. Xenon difluoride

using a near UV lamp [24], xenon and fluorine

and hydra-

[ 111.

was prepared by photosynthesis

xenon hexafluoride was prepared by the reaction between

in the presence of nickel difluoride

as catalyst at 12O’C

[25]. The

purity of both xenon fluorides was checked by i.r. spectroscopy, and in addition, the melting point of xenon difluoride

was determined.

Preparations In a typical preparation into

hydrazinium

fluorometalate

(5 mmoles) was weighed

the reaction vessel and thoroughly dried in a dynamic vacuum at room tempera-

ture. Then an excess of xenon fluoride limation at - 196°C. temperature

(more than 50 mmoles] was added by sub-

The reaction vessel was than slowly warmed up to room

and left at this temperature,

at higher temperatures (up to 140°C],

or in some reactions with xenon difluoride

for several hours. After

the reaction was

completed the reaction products were separately pumped away: at - 196’C at - 80°C

xenon, at - 60°C

hydrogen fluoride and at room temperature

nitrogen,

excessive

xenon fluorides. The mass balance of the experiments were carefully followed throughout the experiment with an accuracy of * 5 mg. The thermal decomposition studies were carried out by following weightloss of the sample when under vacuum as functions of time and temperature.

All

volatiles were trapped and subsequently examined by mass spectrometry and by gasphase infrared spectroscopy. The residual solids in the reaction vessel were chemically analysed and examined by Raman and infrared spectroscopy and by X-ray photography.

TABLE

2

Chemical analysis of XeFe .2AIF3

and XeFe.GaF,

%M calcd.

found

%F calcd.

found

. 2AIF3

13.06

12.7

55.17

53.3

XeFe . GaF3

18.74

20.5

46.97

45.3

XeFe

powder

526 ACKNOWLEDGEMENTS The

authors

this work,

to

Dr.

fluorometalates, diffraction

are grateful P.Bukovec

to

to the

and

Miss BSedej

Research

Mrs. for

Community

A.Rahten

the

for

analytical

the

of

Slovenia

preparation

work,

and to

for

of

Mrs.

support

of

hydrazinium

N.Vene

for

X-ray

photographs.

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