Fluorosulfates of the noble metals, part 4 fluorosulfates of iridium

501

JournalofHuorine Chemistry, 19 (1982) Sol-516 0 Elsevier Sequoia S.A., Lawanne - Printed in The Netherlands

FLUOROSULFATES

OF THE NOBLE METALS,

KEITH C. LEE and FRIEDHELM

Department

of Chemistry,

PART 4a) FLUOROSULFATES

AUBKE

The University

2036 Main Mall, University

OF IRIDIUM

Campus,

of British

Vancouver,

Columbia,

B.C., V6T lY6 (Canada)

SUMMARY The synthesis Ir(S03F)4

and of the ternary

Cs,[Ir(SO,F),]

even at elevated

izations

S206F2,

oxidizing

dependant

ueff obtained

weak antiferromagnetic

(C1D2)2[Ir(S03F)6], The preparative

due to the relative reaction

are slightly

mixture

runs

inertness

of iridium

of bis(fluorosulfuryl)-

acid, HS03F.

spectra

magnetic

and

times, often up to several weeks,

and fluorosulfuric

are based on infrared

on temperature moments

temperatures,

Ir(S03F)3

is described.

by long reaction

the strongly

peroxide,

fluorosulfates

and Ba[Ir(S03F)6

are characterized

towards

of the binary fluorosulfates

Structural

character-

and in case of the Ir(IV) compounds

susceptibility

measurements.

below the calculated

values

The magnetic suggesting

coupling.

INTRODUCTION

In the course of a systematic noble metals and ternary

[1] to [3], we became fluorosulfates

a)

of the

in a study of both binary

In preceding studies [2], [4], we

by bis(fluorosulfuryl)peroxide,

acid, HS03F, as reaction

The preceding the heading:

Cl1 to c31.

interested

of iridium.

had found the metal oxidation fluorosulfuric

study of the fluorosulfates

medium

S206F2, with

to provide a fast and

three publications in this series were published under Fluorosulfates of Palladium Parts I to III. See ref

502 efficient

route to both classes

M + n,* S206F2 m M'S03F

-!?!?3$

of compounds,

M(S03F),

to the schemes

according

and

+ M + n,2 S206F2 -B,

(1)

Mlrn [M(S03F)n+ml

(2)

In case of the alkali metal

with M' = Cs, K or Cl02 as well as others. fluorosulfates,

the reaction

of chlorides

or bromides

found to result

in a simple,

one step synthesis

with HS03F was

of ternary

fluorosulfates

in situ: m M'Cl + M + ni2S206F2+m The role of fluorosulfuric fold:

a) the excellent

accelerate metal,

reactions

made

advantage,

by effectively

We became by selecting resistance

obtained

vessels

on the point

temperatures

must be viewed as an

of the reaction

reaction

vessels,

these reaction

to test the synthetic

oxidizing

reaction

and prolonged

when following

iridium a metal

towards

surface coating

and maintain

temperatures

in some etching

interested

with

was found to be two-

of HS03F was found [4] to

preventing

to achieve

even though elevated

the weights

(3)

liquid range of HS03F with a normal boiling

it possible

were found to result affecting

ability

The use of glass reaction

up to 160°C.

M',[M(S03F)n,,]

acid in these reactions

solvolysing

and b) the wide

of +163'C

HS03F $$$$

times

often quantitatively.

routes described

above

, which had in the past displayed great

agents

[5].

EXPERIMENTAL Chemicals Iridium metal the Ventron

powder,

Corporation.

Chemicals)

was double

previously

[6].

60 mesh of 99.9% purity was obtained

Technical

distilled

at atomospheric

Bis(fluorosulfuryl)peroxide

[8] were synthesized

according

to published

used in this study were obtained purity degree

grade fluorosulfuric

available.

acid (Allied

pressure

as described

[7] and chloryl methods.

from commercial

from

fluorosulfate

All other chemicals

sources

in the highest

503 Instrumentation Details

and Analysis

on our instrumentation

manipulating

volatile

and moisture

of infrared,

Raman and electronic

and the techniques sensitive

substances,

measurements

Gouy apparatus

used in this study has been described

Magnetic

corrections

data on other

All reactions

have been published

were calculated iridium compounds

were performed

fitted with Kontes Teflon

stirring

bars.

of the nonvolatile

Analytische Synthetic

products.

Laboratorien,

[lo].

from reference

[lo].

vials of about 40 ml

was monitored

Microanalyses

The

[9].

constants

stem valves and Teflon

The course of reactions

of magnetic

[2].

earlier

was obtained

in Pyrex reaction

contents

changes

previously

from Pascals

in

the recording

spectra and the calibration

susceptibility

Diamagnetic

employed

coated magnetic

by recording

weight

were performed

by

Elbach, West Germany.

Reactions

Iridium tris(fluorosulfate) Ir + 2S206F2 a Ir(S03F)4

Ir(S03F)4

+>Ir(S03F)3

In a typical

reaction,

(4)

+ l,2S205F2 iridium metal

treated with an excess of S206F2/HS03F of the metal Ir(S03F)4;

initially

metal was formed.

S205F2 and oxygen

(158 mg, 0.822 mmol) was

(%lO ml) at ~140°C.

a deep purple color. a solid which analyzed

had dissolved

Volatile

more S206F2 reheated

was also obtained

at a120"C

in vacua according

together

materials

reverted

to

were removed -in vacua and (398 mg, 0.813 mmol).

by the thermal decomposition to equation

($3 ml) was

at ~140°C.

and the solution

as Ir(S03F)3 was obtained,

Ir(S03F)3

containing

After the removal of most of the

which was subsequently

3 days, all metal

Parts

a deep purple solution

formed from the reaction,

added to the mixture

(5)

to form a brown solution

after 3 days of heating,

with unreacted

After

dissolved

+ li202

(5).

of Ir(S03F)4

In a typical

pyrolysis

504 experiment,

Ir(S03F)4

(294 mg, 0.500 mmol) was converted

into Ir(S03F)3

(239 mg, 0.488) after 12 hours of heating. Ir(S03F)3 solves

is a very deep bluish purple,

in HS03F and decomposes

hygroscopic

solid.

at %200°C with the evolution

It disof a color-

less gas which was not identified.

s

F

39.27

19.66

11.65

39.10

19.46

11.48

Ir

Analysis: Calculated

%

Found % Infrared absorption

bands in cm

14OOs, 121Os, llOOvs,

-1

b, 102Ovs,

with estimated

relative

intensities:

sh, 95Os, b, 8OOs, vb, 63Os, 575ms,

540m and 450m. Iridium tetrakis(fluorosulfate) Ir(S03F)3 Ir(S03F)4

+1/2S206F2

is prepared

Iridium metal

in a reaction

(6) similar

metal had dissolved

cycles of S206F2 addition.

and most of the S 0 F 252

(~2 ml) was added to the solution

in HS03F.

When all the

had been removed, of essentially

Ir(S03F)3

This was heated at +6O"C for 6 hours, after which

a deep brown solution materials

to that above.

(198 mg, 1.030 mmol), was treated with S206F2/HS03F

(~4 ml) using similar

S206F2

--+ Ir(S03F)4

had formed.

The removal of all volatile

by the usual method yielded

the blue Ir(S03F)3 than expected

Ir(S03F)4

with traces of

( the weight of the product was slightly lower

for Ir(S03F)4).

More S206F2

(~2 ml) was added to

this impure product which was heated at 60°C for another The removal

of all excess S206F2

at room temperature Ir(S03F)4

to equation atmosphere

yielded

in HS03F.

(5) at %lOO"C of N2.

6 hours.

(and traces of S205F2 and oxygen)

pure Ir(S03F)4

is a deep brown, almost

is very soluble

time

(607 mg, 1.032 mmol).

black, hygroscopic

It decomposes

into Ir(S03F)3

in vacua but isstable

solid which according

up %15O"C

in an

505 Analysis:

Ir

Calculated

%

Found % Infrared absorption 1390, S,

s

F

32.66

21.80

12.92

32.50

21.60

12.69

bands in cm

-1

and relative

estimated

intensities:

107Os, sh, 102Os, b, 87Os, b, 82Os, b, 64Om, b, 580m

12lOs,

and 540m.

2C102S03F A mixture

+ Ir + 2S206F2 w+

of C102S03F

(%l ml), and S206F2/HS03F

to react with iridium metal All the metal brown. compound

of all volatile

which analyzed

(C102)2[Ir(S03F)6]

b) treating

materials

can also be prepared

conditions,

attack of ClS03F

routes,

for 3 days. became dark

at +70°C yielded

a

(1,362 g, 1.478 mmol).

by:

in reaction

scheme

(7) and proceeding

or

IrC13 with S206F2/HS03F

these synthetic

(~6 ml) was allowed

and the solution

as (C102)2[Ir(S03F)6]

Cl0 SO F with C1S03F 2 3

under similar

(7)

(289 mg, 1.505 mmol) at ~120'C

by that time had dissolved

The removal

a) replacing

(C102)2[Ir(S03F)6]

the required

at ~120'C

for 4 days.

In both

C102S03F

is generated

by an

(formed from the reaction

of IrC13 with S206F2

in

(b)) on the glass reactor. (C102)2[Ir(S03F)6] is soluble

is a dark orange-brown,

hygroscopic

in HS03F and melts with decomposition

solid.

at +19O"C

It

to form

a dark brown liquid. Analysis

Cl

:

Calculated

%

Found %

It-

F

7.69

20.68

12.37

7.51

21.04

12.44

Cs2[Ir(S03F&J CsCl + HS03F -

CsS03F

+

2CsS03F + Ir + 2S206F2 !@&

HCl

(8) Cs2[Ir(S03F)61

(9)

506 was prepared

Cs2[Ir(S03F)6]

by the oxidation

(398 mg, 2.071 mrnol with S2O,F,/HSO3F

of iridium metal

(~10 ml) in the presence

CsCl (798 mg, 4.146 mmol) at ~150°C

for 10 days.

volatile

a product with a weight

materials

correponding

at %70°C yielded

to that expected

Cs2[Ir(S03F)6]

hygroscopic

in HS03F and melts with decomposition

Preparation

(2.121 g, 2.015 nnnol).

solid.

Ba(S03F)2

at +15O"C.

+ HCl

+ Ir + 2S206F2 N

of dried BaC12

(10)

Ba[Ir(S03F)6]

(11)

(198 mg, 0.951 mmol) and iridium metal

(183 mg, 0.952 mmol) was treated with S206F2/HS03F for 2 weeks %16O"C

and, after replenishing

for another

2 weeks.

The removal

a product with a weight

Ba[Ir(S03F)6]

(788 mg, 0.853 mmol).

evident

Ba[Ir(S03F)6] be almost

etching

insoluble

of all volatile

suggesting

at

materials

at

of

is due to the

by the solution.

hygroscopic

in HS03F, and decomposes

S206F2,

the composition

The low yield

of the glass reactor

is a light orange,

(~10 ml) at *lOO"C

the largely decomposed

~70°C yielded

visually

It is soluble

of Ba(Ir(S03F&

BaC12 + 2HS03F -Ba(S03F)2

A mixture

The removal of all

for Cs2[Ir(S03F)6],

is a pale orange,

of

solid.

It appears

to

at %2OO"C.

RESULTS AND DISCUSSION Synthesis Of all the 4d and 5d block metals to show the greatest possible

exception

IrC13 resulted

glass attack

of rhodium

towards oxidation [ll].

in no improvement

The preparative completion,

resistance

while

reactions

so far studied,

Attempts

iridium was found

by S206F2, with the

to replace

the metal

and quite often in incomplete

described

some had to be aborted

caused by irreversible

reactions.

could take up to 1 month eventually

decomposition

by

for

due to extensive

of both the reactant

507 (S206F2) and the solvent

(HS03F).

(>160") was not feasible

since decomposition

than the conversion

of the metal

The S205F2 formed,

identified

A higher reaction

to either

ionizing

ability

of the solvent.

of the solutions,

took place much faster Ir(III)- or Ir(IV)- species.

by i.r. spectroscopy,

before the S206F2 could be replenished

the addition

because

Because

had to be removed

its presence

of the extremely

of the oxidant

least twice after all the metal

temperature

had visibly

was usually

disappeared,

reduces

the

dark colors repeated

at

to ensure complete

reaction. The limited complication. disulfuryl

stability

Its decomposition

difluoride,

reoxidation

S205F2,

and decomposition

the oxidizer elevated

thermal

into fluorosulfate

radicals

-

These difficulties

with formation

to equation

accounted

build up during

of 02 and

(5), followed

by

for the consumption

reactions.

had been found to dissociate

Normally

of at

reversibly

[12]:

(12)

also affected

the [Ir(S03F)6] 2- ion .

containing far

according

an additional

2.50 F 3

-

s2°6F2

S206F2

presented

into Ir(S03F)3

cycles,

and the pressure

temperatures

of Ir(S03F)q

the synthesis

This species

of complexes

appeared

to dissociate

more readily in solution than in the solid state. Ba[Ir(S03F)6],

did not dissolve be obtained

at reaction

a presumably

which were to obtain

always

attempts to synthesize

vessel.

Evidence

of the final reaction

lower than expected complexes

but

temperatures,could

had to be abandoned

of the reaction

in the weights

fluorosulfate

of +16O"C,

Na2{Ir(S03F)6]

corrosion

was found

in HS03F even at elevated

temperatures

more soluble

due to extensive corrosion

appreciably

(see Experimental

of Ir(II1) were

which

after one'month for such

products, section).

Attempts

unsuccessful.

In summary the reactions described here pointed clearly to the limitations

of our synthetic

method.

All reactions

were extremely

time

508 consuming

and required

The formation

rather

of oxygen

large quantities

during

the reactions

of bis(fluorosulfuryl)peroxide. required

constant

monitoring

in order to avoid explosion. Vibrational

Spectra

Due to the intense spectra

dark colours of b,oth binary

could not be obtained.

resolution

and use of fluorocarbon

improvement.

The observed

section without

resolution

complexes,

comparison

frequencies

complexes

type of metal-ligand

an ionic formulation it appears

study have octahedral

Magnetic

Susceptibility

Not unexpectedly a spin paired

monoclinic

at

80 K [13].

are listed in Table [14].

1 in

The three

to that of Cs2[Pt(S03F)6], and a monodentate

of the three vibrational -1

that all the iridium

in the i.r. spectrum

for iridium,

species

involved

with bidentate

in this

S03F-groups

fluorosulfates.

However

by comparison

TIP contributions

color

for the compound.

Ir(S03F)3

mO1 -' a small contribution Similar

in no

Measurements

d6 system.

cm3 mol -', suggests

1060 and 522 cm

coordination

for the two binary

recorded

interaction

The positions

of the S03F-groups.

In summary,

evident

resulted

of reasonable

of Cs2[Pt(S03F)6].

that are similar

n-odes of ClO2+ at (1310, 1295), indicate

i.r. spectra

of these compounds

have spectra

a similar

coordination

poor

have been listed in the experimental

poor qualitywere

with the Raman frequencies

suggesting

agents

but due to their deep yellow

of only relatively

The vibrational

oils as mulling

Raman

interpretation.

could be obtained,

Raman spectra

spectra were of extremely

band positions

For the [Ir(SO,F),]*-

iridium

Infrared

fluorosulfates

is found to be diamagnetic, the experimental

have been observed

forms of IrC13 [lo].

x, value of (-80+30)~10-~

with the calculated

from temperature

suggesting

value of -154~10~~

independent

paramagnetism

for both the rhombic

cm3

(TIP).

and the

509 TABLE

1

Vibrational

frequencies

complexes.

IR

R

IR

R

1400,138Ow

1390sb

1415~

1390s

1416w,sh 1410m

1250~s 1200w 1047s*

1195s,b

1255m 1212~

1200s

R+

IR 1400s,b

of [Ir(S03F)6]2-

131os* 1295s*

1200s 105ow* 950vs,vb

1057m 950vs,b 978w 920vs,b 950w -8OOs,b -802w,b

125ovs 1219m 1043s 1OlOm

950s,b 900s,b 820s

%800w,b

820s

840,810~

660s

640~

645m

630~

630~

634~s

590s

580~

570s

575w

575m

579vw

550s

548~

540s

550w

540m

55ovw

522m*

52Ow* 460~ 440m

440w

460w,sh 447m

440m

460~ 443w

* denotes

bands due to C102+

' obtained

at

80k

IR denotes infrared band positions,

For Ir(S03F)4 result

ground

(IV)

Raman shifts.

a spin paired d5 system would

an assumption

hexakis(fluorosulfato)iridate susceptibility

R denotes

and its derivatives

2 in a T2g groundstate,

magnetic

280~s

287~

286m 268m

seemingly

complexes.

justified

According

for the

to Figgis,

the

2 of a d5 low spin system with a T2g electronic

state can be represented

U2 = 8 + (3x -8)exp(-3x/2) x12 + exp(-3x/2)]

by the equation

[15]:

(13)

510 where

x = i/k1

X = -E,= -5000 cm k = Boltzmann's

This would

imply,

temperatures)

-1

constant

decrease minimum

-,

4,

have values

cm-'

(for large

with

from 1.76

temperature,

value predicted

drops at temperatures to antiferromagnetic The magnetic

coupling

The difference for Ir(S03F)4

(13).

results

the observed

the

also showed marked

[lo].

on (C102)[Ir(S03F)6]

(the estimated

magnetic

uncertainty

is most pronounced

2 respectively.

compounds.

primarily

the [IrC16]'-

and the Curie-Weiss

moments

moments

found

on the two hexacation dependance ion [ll], [16]. are relatively

2, implying

for

approximate

12 and 28K.

behavior

coupling,

are lower than

law seems to be followed

This gives 1,x,c values as shown in Table between

The

in p is about +0.02uB).

The observed

As can be seen from Fig. 1, the magnetic of temperature

moments

for the magnetic

will center

of u is also found for salts containing

ferromagnetic

For the

of their peff is shown in Fig. 1.

kis(fluorosulfato)iridate(IV)

The magnetic

K),

lower than A,

The moments

are listed in Table

and the discussion

Weiss constants

(%lOOto330

of Ir(IV), ueff was found to generally

in the system

susceptibility

values

in this study

below $150 K to al.3 uB; this had been attributed

dependence

the expected

K.

moment

~8 at 100 K to 1.84 pB at 330 K.

by equation

In all three cases,

T>150

the magnetic

but in most cases they were

and Ir(S03F)4

Cs2[Ir(S03F)6]

independent

1x1 values or at very low

while as x -0,

range accessible

and hexabromocomplexes

temperature

constant,

a value of a

In the temperature

hexachloro-

= 0.6950

as x approaches

!-I would approach

may approach

u should

for Ir(IV) [5] = spin orbit coupling

found may best be rationalized

an explanation

also favoured

by assuming

for the [IrC1612-

antisalts.

511 TABLE

2

Magnetic

Properties

of (C102)2[Ir(S03F)6],

Cs2[Ir(S03F)6J

T

X"CXlO3

[K]

[cm3 mol]

[cmm3 mol]

107: 130

4.348 3.236 2.653

230 309 377

'/Xmc(calc'd) = (T+l2)/0.382

178 155 203 227 251 276 300

2.294 2.000 1.770 1.585 1.447 1.326 1.238

cs,[Ir(so,F),jl

78 106 129 154

3.831 3.003 2.494 2.141

203 179 229 252 277 302

Jr(S03F)4

l/X,n~ (calc'd) = (T+l9)/0.262

(:+28),0.395

Explanation:

436 500 565 631 691 754 808

436 498 563 626 689 755 816

1.68 1.69 1.70 1.70 1.70 1.71 1.72

1.68 1.69 1.70 1.70 1.71 1.71 1.71

269

1.681 1.880 1.536 1.410 1.290 1.214

261 333 401 467 532 595 651 709 775 824

339 399 462 524 586 651 709 773 836

1.55 1.59 1.60 1.62 1.64 1.65 1.68 1.68 1.69 1.71

1.52 1.58 1.61 1.63 1.65 1.66 1.68 1.68 1.69 1.70

284 254 230

0.906 0.963 1.028

1104 1039 972.9

1155 1040 948.9

1.43 1.40 1.38

1.40 1.40 1.39

205 177 154 130 107 78

1.102 1.302 1.556 1.758 2.044 2.963

907.7 757.5 642.8 569.1 489.3 337.5

853.5 746.7 659.0 567.5 479.8 369.1

1.34 1.37 1.38 1.35 1.32 1.36

1.39 1.38 1.37 1.35 1.34 1.30

corrected

= Bohr Magneton,

peff = effective

of antiferromagnetic

As the vibrational

complexes

show great similarities,

undertaken.

in K;

Xmc = molar magnetic -1 in cm3 mol ,

for diamagnetism

magnetic

moment

values

further.

experiment

a)

1.63 1.66 1.67

of measurement

[cm-3 mol]

Ueff

1.64 1.67 1.66

a) calculated

dilution

Ueff

234 314 371

susceptibility,

The possibility

a)

111B3

T = temperature

VB

XmC

[v,]

(C102)2[Ir(S03F)6]

1,x c (calc'd) =

VXmc

and Ir(S03F)4

involving

spectra

coupling,

was .therefore investigated

of the [Ir(S03F)6]2-

and similar

a mixture

structures

and [Pt(S03F)6]2as expected,

of (C102)2[M(S03F)6],

M=Ir,Pt,

a was

512

calculated,

eqn. (13)

ueff

l

cs2[Ir(S03F)61

+ (c102)2tIr(S03F)61

l.oUB

’

a

1

100

1

200

300

Temperature FIG.

1. MAGNETIC MOMENTS

Starting

OF (C102)2[Ir(S03F)61

with a mixture

of metal powders

iridium,

the mixed chloronium

C102S03F

and S206F2/HS03F.

and had the appearance magnetic

susceptibility

comparatively

measurement

also ensures correction

complexes

The presence

the formation

of (250 15)~10-~

over a temperature

product

weight

The result of a bulk is given

in Table

3.

in the case of

that can be prepared

of an excess

Of a highly

the metals with

has the expected

were used because, complex

8.85 mole % of

by reacting

on the mixture

it is the only iridium easily.

containing

of (C102)2[Pt(S03F)6].

The C102-containing [Ir(SO,F),]*-,

AND Cs2[Ir(S03F)61

salt was prepared

The resulting

[K]

of C102S03F,

pure product.

cgs units, obtained

The diamagnetic

for (C102)2[Pt(S03F)6]

range of 81 to 300 K, was used for both the complexes.

513 TABLE3 Magnetic

properties

of (Cl02)2[Ir(S03F)6]

diluted

in (C102)2[Pt(S03F)6]

(8.85 mol% It-) T

x; x 103

CKI

[cm3mol_'1

303

1.506

277

l/X;

l/X;

Peff(calc)

Peff

(talc.)

h,l

ha

664

728

1.91

1.82

1.515

660

675

1.83

1.81

251

1.435

697

621

1.70

1.80

229

1.616

619

575

1.72

1.78

204

1.911

523

523

1.77

1.76

179

2.201

454

472

1.78

1.74

154

2.416

414

420

1.73

1.71

129

2.745

364

369

1.68

1.67

106

3.073

325

320

1.61

1.62

78

4.049

247

263

1.59

1.54

Any Temperature estimated

Independent

present

in these systems,

to be of the order of only 50~10-~ cm3 mol-'

compensated

[15] should

be

for by this procedure.

Although

the accuracy

the introduction majority

Paramagnetism

of the measurements

of the diamagnetic

constituent

weight measurements,

(the estimated

(C102)2[Pt(S03F)6],

uncertainty,

by

as the

arising mainly

agree well with those calculated

are consistently

from

from equation

higher than those of pure

(ClO2)2[Ir(SO3F)6]-

Thus antiferromagnetic

Ir(IV) fluorosulfate

system,

to a lowering

reduced

ranges from *0.12 PB at $300 K to +0.05 uB at 80 K),

the values of ueff obtained (13), and in general,

species

is greatly

coupling

does occur

in the

and is the most likely cause contributing

of Peff in these compounds.

Similarly

the low ueff values

for Ir(S03F)4 may at least in part be due to antiferromagentic a process more likely in a polymeric,

fluorosulfate

bridged

coupling,

compound,

than

514 in the anionic the presence

complexes

discussed

of antiferromagnetism

of the range of measurement certain

above.

While our data suggest

in these Ir(IV) compounds,

down to 4 K would

be required

strongly

an extension

to be completely

about the extent of such coupling.

Solution

Studies

in HS03E

The isolation iridate(IV)

and identification

complexes

suggest

of the hexakis(fluorosulfato)-

that Ir(S03F)4

may act as a fluorosulfate

iol

acceptor:

Ir(S03F)4

and possibly

+ 2SO3F-

even as an ansolvo

the difficulties to detailed

in obtaining

(14)

CIr(S03F),12-

e

acid as does Pt(S03F)4

Ir(S03F)4

[14].

present a substantial

However obstacle

studies.

We have therefore

restricted

The conductivity

investigation.

ionic dissociation

according

our studies data listed

to an exploratory in Table 4 suggest a simple

to:

(15)

similar

to results

CIr(S03F)J

2-

Solutions

and suggest

existence

of

in HS03F solution.

Interestingly absorption

for (C102)2[Pt(S03F)6,

spectra

Ir(S03F)4

and (C102)2[Ir(S03F)6

in HS03F with a very intense

of Ir(S03F)3

show a similarly

give identical

band

(E

~10000)

at 200 nm.

strong band with hmax at 563 nm.

It seems likely that these bands are due to ligand -t metal charge Their

intensity

and broad band shape prevent

due to d-d transitions.

the observation

transfer.

of bands

515 TABLE

4

Conductivity Cont.

of (Cl02)2[Ir(S03F)6]

x lo2

[mol x kg-']

in HS03F* at 25.O"C.

k(spec/cond.) x lo4 -1 cm-'] [ohm

Cont. x lo2 [rool x kg-']

K(spec/cond.) x 104 -1 [ohm cm-']

0.00

0.280

1.40

19.60

0.20

3.801

1.60

21.50

0.40

7.581

1.80

23.60

0.60

9.885

2.00

25.63

0.80

12.20

2.20

27.49

1.00

14.92

2.40

30.06

1.20

17.56

2.60

32.22

cont. in mol x kg * interpolated

-1

K = specific

x 102

conductance

in ohm

-1

cm

-1

ACKNOWLEDGEMENT Financial Council

support

by the Natural

Science

of Canada in form of an operating

ship to one of us (K.C.L.)

is gratefully

and Engineering

grant and a postgraduate acknowledged.

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2

K.C. Lee and F. Aubke,

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3

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4

P.C. Leung and F. Aubke,

5

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6

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A suitable

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compounds.

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B.N. Figgis,

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