JoumalofFluorine Chemistry, 20(1982)107-119 107

Received: June 25,1981,

Zirconium(IV)Fluorosulphat~ : --- - Preparation and Characterization

* SUKHJINDER SINGH, MANINDER BED1 and RAJANDER D. VERMA

Department of Chemistry,Panjab Universlty,Chandigarh-160014(tidia)

SUMMmY

Zr(S03F)4,.(A); ZrOGN3F>,, @I; zr(02CCH3),G03F),, (Cl;

and Zr(02CCH ) SO F,(D) 33 3

have oeen prepared and characterized

(elemental arialysis,i.r. spectra and thermal analysis). The

S03F groups are bidentate in (A) - (C) but have C3V symmetry in

D where all the three oxygen atoms of dti3F group are coordinated

in an equivalent manner. (A) - (D) are good Lewis acids and

form coordination complexes with pyridine, triphenylphosphine

oxide and 2,2'-bipyridyl. The thermal decomposition of the

fluorosulphates is complex.

INTRODUCTION

ZrF3S03F is

presently reported

the only zirconium(IV) fluorosulphate

(11. In continuation of our work on

fluorosulphates [2-u, we now report the preparation and

characterization of the novel zirconium(IV) fluorosulphates,

Zr(S03F)4,(A); ZrO(S03F)2, (B); Zr(02CCH3)2(S03F)2,(C); and

Zr(02CCH3)3S03F,(D). Comijounds C and D are to our knowledge

the first examples of compounds having S03F and acetate groups

in the same species. Some coordination complexes have also

been prepared and characterized.

0022-l 139/82/0000-0000/$02.75 OElsevier Sequoia/Ynntedin The Netherlands

108

Materials --

Zr(02CCH3)4 was prepared by the action of a SO:50

mixture (by volume) of acetic anhydriae and acetic acid 'on

hydrated Zr(iv03)4. Anhydrous ZrOC12 was obtained oy dehydrating

its octahydrate with thionyl chloride [s]. Zr(02CCF3)4 was

prepared by anion exchange,i.e., reacting Zr(02CCH3)4 with

trifluoroacetic acid at refiux temperature. Fluorosulphuric

acid was prepared by the reaction of SO3 with KHF2 and purified

as reported previously (6.). Pyridine, (Py) and solvents were

purified as described in the literature /7]. 2-2' bipyridyl,

(bipy), (B.D.H., A.R.), triphenylphosphine oxide, (TPPO),

(E.Merck) and sulphuryl chloride (E.Merck) were used as such.

Tetra(fluorosulphato)zirconium(lV),(A) ------ -

Excess (5-6 fold) fluorosulphuric acid was distilled

onto 3.04 gms (5.6 mmol) of Zr(02CCF3)4. The mixture was

stirred magnetically for 10 hours at room temperature under

nitrogen. The white solid formed was filtered under a positive

pressure of nitrogen, washed repeatedly with fluorosulphuric

acid followed by sulphuryl chloride and finally dried in Ivacuo'.

Bis(fluorosulphato)oxozirconium(IV),(B~

Excess (5-6 fold) fluorosulphuric acid was distilled

onto 0.961 gms (5.4 mmol) of anhydrous ZrOC12. The mixture

was refluxed under nitrogen till evolution of HCl ceased.

The white solid formed was filtered, washed and dried as above.

109

Bis(acetato)bis(fluorosulphato)zirconium(IV),(C)

Freshly distilled fluorosulphuric acid (0.868 gms,

8.68 mmol) was added to the suspension of Zr(02CCH3)4 (1.419 g,

4.34 mmol) in 50 ml. sulphuryl chloride. The mixture was

stirred for 5-6 hours at room temperature. The white solid

formed was filtered, washed and dried as above.

Tris(acetato)(fluorosulphato)zirconium(IV),(D)

Zr(02CCH3)3S03F was prepared as for C using HS03F

(0.482 g., 4.82 mmol) end Zr(02CCH3)4 (1.576 g., 4.82 mmol).

It was washed only with SO2C12 end dried in 'vacuol.

Preparation of complexes

The complexes A.4Py, A.4TPP0, A.(bipy)2, B.2Py,

B.2TPP0, B.bipy, C.2Py, C.bipy, D.Py and D,.bipy were prepared

by stirring a suspension of A, B, C or D in an appropriate

solvent (CC14 for pyridine complexes end benzene for others)

with the ligand in the required stoichiometry for about 14 hours

under N2. The adducts formed were filtered under N2, washed

with solvent end finally dried in lvacuoI. Complexes of the

same stoichiometry were obtained even when the ligands used

were in excess.

Analytical Methods and Instrumentation

Zirconium was determined as Zr02 gravimetrically after

decomposing the complexes with concentrated nitric acid and

igniting the residue. Sulphur end fluorine were determined

as reported earlier [2,3]. Carbon, hydrogen and nitrogen were

determined microanalytically. The analytical results are

given in Table 1.

110

TABLE 1

Analytical Data

A 18.h 26.9 (18.7) (26.9)

B $8:;)

C 22.6 (22.4)

If 24.8 (24.8)

A.4Py 10.9 (11.3)

B.2F'y 20.2 (19.65)

c.2Py 16.4 (16.1)

a*m 20.6 (20.4)

A- (Wv I2 (‘1:: > t B.~PY 19.5

(19.7)

C.bipy 15.6 (16.2)

D,.bip~ 21.1 (20.45)

LbTPPO 6.0. (5.7)

B.PTPPO 10.7 (10.6)

21.2 (21.0)

16.1 (15.7)

$79)

16.1 (15.9)

14.1 (13.8)

i%

t5:L

16.3 (16.0)

14.1 (13.9)

11.8 (11.4)

Z)

J:iZ,

t;: ) %

12.4 (11.8)

20.2 (19.6)

30.6 (29.9)

30.5 (29.7)

28.6 (29.6)

30.5 (30.0)

26.8 (26.0)

30.9 (29.8)

30.8 (29.7)

*Theoretical figures in parentheses.

111

The infrared spectra of the compounds were recorded

as nujol or hexachlorobutadiene mulls between &Cl, NaCl end

polythene plates using a Perkin-Elmer 621 spectrophotometer.

Thermal analysis was carried out by means of a MOM/Budapest

derivatograph (type : Paulik, Paulik and Erdey) at a heating

rate of s'C/minute. All manipulations were carried out in a

dry box filled with dry nitrogen.

EESULTS AND DISCUSSION

Fluorosulphuric acid reacts with Zr(02CCF3),+ exothermally

at room temperature to give A. The reaction temperature

was maintained below 1O'C. The reaction between fluorosulphuric

acid end tetra(acetato)zorconium(IV) in 2:l or 1:l ratios at

ro3m temperature in SO,Cl, yields C end D respectively. D was

converted to C by reacting it with an appropriate amount of

HS03F below 35'C. The reaction of Zr(02CCH3)~ with an excess

of HS03F at room temperature also yields C. Compounds without

definite stoichiometry were isolated, when Zr(02CCH3),+ and

HS03F were refluxed. Anhydrous ZrOC12 reacts with fluorosulphuric

acid on reflux to give ZrO(S03F)2. All of these fluorosulphates

are white hygroscopic solids insoluble in noncoordinating

solvents and in BS03F.

Infrared Spectra

The i.r. spectra of fluorosulphates (A - D) in the

region 4000-200 cm -1 with their tentative aSSi@metItS are

tabulated in Table 2. Bidentate fluorosulphate groups are

postulated c8-111 in A, B and C based on the observation of

three S - 0 stretching frequencies : [A : l-395, 1140 ( *asSO),

Table 2

1K Cata

zr(S03F)4

ZrO(S03F)2

Zr(02CCH3)2G03F)2

Zr(02CCH3)3S03F

Zr(02CCH3)4*

Assignments

1395

m il

4Omb

lc60s

1340

s 13

5om

1liOmb

iC'~0mb

5653~

835.

5 85

5s

65Om

59Om

55om

tiow

320w

295~

620~

58Om

545m

Et:

2yOsb

*Ref.15

2Y34

m

162Oms

148Om

1340

m

1135m

1065s

1025mw

440m

820~

665~

575s

525~

1

455m

35

5w

2925m

2380

~

1710

s 16

75~

i625m

1400m

1220vs

1115s

102Om

980m

850m

66Ow

600111

530m

s

430s

295m

s

2930

CH sym. stretch.

154-

o

1455

'as"

bp

J)+(

E)

“, (

A,

1

CH3 rock.

M"- 0 vibrations

C-

C stretch.

*,(A,!

CO2 sy~!,.def.

J5W

Q3 (

A,

1

1’6(

E)

M - 0 Lattice

vibrations

113

1060 ( $SO); B : 1390, 1110 ( 3asSO)' 1070 ( 9sSO); C : 1340,

1135 ( *asSO), 1065 ( $W). The S-F and S-O bending frequencies

are listed in TABLE 2. & weak broad band centred around

965 cm-' in B is attributed to zirconium-oxygen vibrations

having a bond order between one and two (12,.l3). An isolated

H&I group generally has a strong sharp band in the region

of 900-1050 cm -l (141. The magnitude of 09 ( *,CO- $CO) in

C(140 cm-l) indicates bidentate bridging acetate groups (151. .

The peaks at 1710, 1675, 1625 and 1400 cm-' (assigned to

asymmetric and symmetric stretching carbonyl frequencies)

in D indicate the presence of monodentate as well as bidentate

acetate groups (15). Two strong bands at 1220 and 1115 cm-l

in D are assigned to a fluorosulphate group having C3F symmetry

with the three oxygens of the fluorosulphato group coordinating

to the zirconium equivalently (16,171.

On comparing the i.r. spectra of C and D with those of

Zr(S03F)4 and Zr(02CCH3)4, Table 2, it is evident that

C and D are not simple mixtures, but are definite novel

fluorosulphate species.

The three S-O stretching frequencies (-1410, cl260

and ~980 cm -1

> and a single value of S-F ( -810 cm") in A.4Py,

A.4TPP0, A. (bipy)2, C.2Py and C.bipy., indicate the presence of

monodentate fluorosulphate groups 1181, whereas bidentate

fluorosulphate groups are indicated on the basis of es_o

frequencies (wl350; rc.1170 and ~1110 cm-l) in D.Py and

D2.bipy. The frequencies ( ~1400, bl370, a1150, 111080 and

N 990 cm") of the S-O vibrations and two different values of

S-F ( "805 and ~850 cm-') indicate monodentate as well as

bidentate fluorosulphate groups in B.2Py, B.PTPPO and B.bipy.

114

The appearance of a weak band at 111235 cm-l and upward

shift of bands at 1578, 601 and 403 cm -1 to ~1605, ~6640 end

PJ 430 aI+ . In pyridine complexes indicates the coordination

of pyridine to zirconium [19J. A peak which is not present

in free bipyridyl., but has been found in several chelated

complexes [201, appears at s. I325 cm -' and a peak at 990 cm"

is intensified and shifts to ca. 1925 cm-l in its adducts

with A, B and C. On chelation, the 402 ctn'l band of bipyridyl

shifts to ~a. 415 cm -l (211. -1 A peak at ~1320 cm found in

several chelates of bipyridyl is not observed in D2.bipy.

However, the ring vibration bands of the free base at 1580,

1558, 1540, 1522 CR? shift to 1610, 1585, 1565 and 1550 cm -1

in D2. bipy. Lowering of epzo (1190 cm-l) in free base to

E. 1120 cIz+ in the complexes indicates that coordination

occurs through oxygen in case of the triphenylphosphine oxide

complexes [22J.

It is difficult to make very meaningful assignments

for acetate groups in case of complexes of C and D with

pyridine and bipyridyl, as pyridine and bipyridyl complexes

have a number of strong bends in the region 1425-1630 cm-l.

Thermal analysis

TG and DTG cur@es recorded in the presence of air

show the thermal decomposition of A - D as a process consisting

of several steps (Fig.1). DTG minima have been projected onto

the TG curves to get various inflexion points.

The probable modes of decomposition resulting from

these curves -are given in scheme I. The number on the arrow

heads indicates the observed percentage veight loss for that

step with the theoretical values in parentheses. The

115

II0

5 70- !?

!z 60

t

t 50

t

t 40

t

t

t 47-- ,

’ 1 900 1000 201 I I 1 I I 1

0 IQ0 200 300 400 500 600 700 i3oc

TEMPERATURE (“Cl

Fig. 1 THERMAL DECOMPOSITION OF COMPOUNDS A,B,C 8\ D

116

A: Zr(SO3Fj4 20.7c20.9 %I >

go-290°c ZrS04(S03F)2

I -S02F2

4.2(74.7_+ ZrO2 72o-895’c

4 so3

B: 10.601.1 %,> >

3ZrO@03FJ2 85 - 1goOc

Zr303(SC3F)4SO4

I -S02F2

3Zr02 <m 2Zr02 + 74.0~glo"c 1 V

-so 3

-2S02F2

-2s03

c: 4Zr(02CCH3)2(S03F)2 13.1 (12.5 %I, go-245Oc

Zr402(02CCH3t13)4(S03F)8-

-2(CH3CO)20

2Zr02 +J,.ZrOS044 5g*o(5g'g skii . 1.9;

v -1 570-735OC zr404(so4)3(so3F)2e2$_57~OC

-2(qi3Co)2'

-3SO2F2

SCHEME 1

117

D: 3zr (02CCH3 )3S03F 24. ,,‘:;;;‘, ‘) ) zr3°2S04(o~C~3 )4@‘3’)2)

-2(cH3co)20

-CH3COF

3Zr02 *k Zr303S%(02CCD3)2(S03F)2 < 33 7W.4 $ 470-900 Oc 35b470%

denominator shows the probable molecules eliminated and the

temperature range in which the decomposition takes place.

The deeoeposltlon starts at ~a. 90°C in A, B end C but

at 7OoC In D. In all the four uases, the weight and

analysis of the final residue corresponds to the formation of

Zr02. In B (curve b), the percentage weight loss is only 3.4 f

from 200-5OOoC. To understand this step, oompound B was

heated separately at 13OoC (maximum loss in weight) under

vacuum (10 -3 torr) and the residue and volatile8 were examined

separately, SOg2 was found as the volatile speoies and

analysis (Calc. for Zr303(S03F)~S0~ t Zr, 33.6; S, 19.7; F, 9.35~

Found t Zr, 33.1; 8, 19.8; F, 9.0 j6) and i.r. of the residue

Indicate an empirical formula Zr303 (S03F)4f304. ‘Ihis intermediate

was habIke up to

evolved In A and

Volatile8 fr@m D

residue contains

The formation of

about 50OOC. The nature of the volatile8

C (soheme I) was confirmed from their 1.r. 8pectra.

show cH3COF and (CF13CO)20 and from i.b., the

fluorosulphate and acetate groups (step 1).

a mixture of Zr02 and ZrOS04 has been observed

In A, B and C prior to the formation of the end product Zr02.

This step Is not obserred In D, where the intermediate

Zr303g04(CX3COO)2(S03F)2 decomposes in a single step to give Zr02.

118

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