- Email: [email protected]
Cyclic sulphoxides as ligands. 1-adducts between lanthanide perchlorates and tetramethylene sulphoxide (TMSO)
INORG. NUCL. CHEM. LETTERS Vol. 7, pp. 967-972, 1971. Pergamon Press. Printed in Great Britain.
CYCLIC I-ADDUCTS
SULPHOXIDES
BETWEEN
AS LIGANDS.
LANTHANIDE
TETRAMETHYLENE
PERCHLORATES
Lea B . Z i n n e r
and G.¥icentini
(Received 18 J ~ e f
Departamento Instituto
AND
(T~SO).
SULPHOXIDE
.
de Qulmlca
de C u [ m i c a , U n i v e r s i d a d e
1971)
Fundamental
de Sao P a u l o , S . P a u l o ,
Brasil
INTRODUCTION
Adducts and
dimethysulphoxide
LnC15.
x DMSO
Ln(N03).
(DHSO)
(x = 3,4)
x DMSO
(3)
preparation
of
sulphoxide.
Compounds of
Pr,
Nd,
the
lanthanide
Sm, Eu~ G d ) ,
L n ( C I 0 4 ) 3. and
(1),
were
L n ( C I 0 4 ) 3. described
in
In
this
perehlorate
the
lanthanide the
y DMSO
(y = 7 , 8 )
we
Lu)
anti
the
tetramethylene
8 TblSO (Ln = L a , Dy,
were obtained. have
(2)
present
with
THSO (Ln = T b ,
in nitromethane
salts
compositions
literature.
note
L n ( C I 0 4 ) 3.
Ln(C104)3.7.5
conductances
to
adducts
composition
7 THSO (Ln = Tm, Yb,
molar
between
corresponding
Ho,
Er,
The i . r .
Ce,
Y) a n d spectra
been determined.
EXPERIMENTAL Preparation dissolved a small
of
(1:8) Inc).
volume of
chloride
adducts.
in a sufficient excess
Laboratories small
the
to
of
amount
lanthanide
of absolute
tetramethylene
The s o l i d
ethanol
constant
The h y d r a t e d
adducts
and dried
in
weight.
967
ethanol sulphoxide
were collected, vacuo
over
perchlorates and
treated
(from washed
anhydrous
were with
K and with
K a
calcium
968
CYCLIC ~JLPHOXIDES AS LIGANDS
Analytical aqueous
procedure.
solution
(Amberlite
of
IR-120
performed
The
spectrophotometer
Carbon
using
a
the ions
determined cationic
liberated
were
and hydrogen
Nujol
mulls
for
resin acid
standard
by
the usual
microanalyses
a
were
Laboratorium.
Perkin-Elmer
the
an
column
with
determined
MikroanaIytisches
with
by p a s s i n g
adducts
and a
25,00
~ 0~020C
~lodel
557
film
for
KBr p l a t e s .
Condutance
measurements.
Industrial
Instrument
and Northrup
titrating
were determined
ligand~between
were
compound through
Bernhardt
These
ions
lanthanide
method.
by A l f r e d
I~r.spectra.
the
the
II +) a n d
sodium hydroxide. oxalate-oxide
Perchlorate
VoL 7. No. 10
cell
These
w e r e made a t
~ l o d e l RC-16B c o n d u c t i v i t y
(K c = 0 , 1 0 7 0 8
bridge,
with
an
using
a Leeds
of
adducts
analytical
data.The
cm-1).
I~ESULTS :~ND DISCUSSION
Three were
obtained.
Table
compounds are benzene,
slightly
and quite
that
all
in acetone
adducts
Infrared
spectra,
to
frequencies
lower
;ind a s t r o n g ) J that is
not
bonded
composition li~and ions.
spectrum
of
is
The d a t a 1:3
the
to
tile
presented
i n an
.qhift
of
intermediary the
i.r.
the
and
Figure
of
( 50 c m - l ) .
ion.
the
chloroform
2
indicate
S--O s t r e t c h i n g
The v e r y
ion are and
that
position data
in Table
the
2 a typical
of
spectrum
3
band
indicating ion
compounds of
two
Figure
mode
perchlorate
one molecule
between
obtained,
strong,}
observed,
that
Tile e x i s t e n c e
T~ISO i n d i c a t e
3 contains li~and
and
and
in nitromethane.
perchlorate
lanthanide
Ln(Cl04)5.7.5
tetrachloride
nitrobenzene
electrolytes
o!)served
for
the
in carbon
s y m ~ l e t r y was m a i n t a i n e d
may l i e table
are
types
and nitromethane.
h considerable
l band
tetrahedral
summary of
in methanol,
measurements.
the
a
insoluble
soluble
soluble
Conductance
1 contains
practically
different
of
the
lanthanide 1 contains of
the
an a d d u c t .
12,20
12,83
15,08
13.25
13.41
::d (C l ~) | ) 3,8T,~ISO
Tb(C104)5.7.5fHS0
Dy(CI04 ) 3 , 7 . 5 T M S 0
lto (C104 ) 5,7,5T,~ISO
Er(CIO4)3.7.5TMSO
Y(C104)5,7,5L~ISO
7.60
14.55
11,84
E u ( C I 0 4 )3.8T~130
Lu (C104)3.7TMSO
II ,73
Sm(C104) 3.8T~ISO
14.12
11.30
Nd( (" 104 ) 3.81'tqS0
14.41
11.07
Pr(CIO4)5,8IHSO
l'b (C104)3.7TMSO
11,02
Ce(C104 ) 3.87~[50
~m(CIO4)3.7rMSO
]0.93
Theor.
La (C104 ) 3,8T,~IS0
Compound
Ln
7,55
14,53
14,42
14,01
13,60
13.35
15.00
12,65
12,24
11,92
11.83
11.25
11,05
11.12
11.05
Exp.
Summary
1
25,53
24.81
24.85
24,94
23,93
23,97
24,02
24,09
23,15
23,24
25.27
25.38
23,44
25,46
23.48
Fheor.
ClO 4
25,42
2.4,62
24.37
24,76
23.95
23.94
23,96
24,06
25,10
23,34
23.28
25.37
23,42
25,20
23.50
Exp.
~nalysis
of analytical
TABLE
C
50,84
27,97
28,01
28,11
28,90
28,95
29,01
29,09
29,82
29.94
29.98
30.12
30,20
30.22
30.25
Theor.
(%)
results
50,79
28,13
28,06
28,28
28,66
29,02
29,13
29,27
29,85
30,01
29.82
50.15
50.3t
30,38
30.35
iLxp.
5,18
4,69
4,70
4,72
4,85
4.86
4,87
4.88
5,03
5,03
5.03
5.06
5,07
5,07
5.08
Theor.
H
5 21
4 79
4 69
4 67
1 85
4 87
4 98
4 88
4 87
4 90
5. I 0
5 .i0
5 .06
5 .19
5 .07
Exp.
z
r
o
g-
r-
q
970
CYCLIC
SULPHOXIDES
AS LIGANDS
TABLE Electrolytic
2
conductance
Compound
Concn.
V o l . 7, N o . 1 0
in nitromethane
m mole
../k.m ( m h o ,
cm 2,
La(CI04) 3. 8 THSO Ce(Cl04) 5. 8 TMSO Pr(Cl04) 3. 8 TMSO Nd(CI04) 3. 8 TMSO Sm(CI04) 3. 8 TMSO Eu(CI04) 3. 8 TMSO Gd(CI04) 3. 8 TMSO Tb(CIO4)3.7.5THSO Dy(CIO4)3.7.STMSO Ho(CIO4)3.7.5THSO
0,99
220
0,82
222
0,96
224
0,91
215
0 89
228
0 96
221
88
222
Er(CIO4)3.7,5THSO
0
0 96
225
0 92
230
0 90
248
0 93
226
? TNSO
1
22
227
Yb(CI04)3.
7 ~MSO
0 93
230
Lu(CI04)5.
7 EHSO
0 99
225
1 07
223
Tm(CI04) 3.
Y(ClO4)s.7,5THSO
75 I00
8.0
90
'
'
I0,0
MICRONS
13.0
15.0
mo1-1)
20,0
25.0
80 A
uJ 60 Z I,.-
I-40I,-
2O
0
l
I
|
|
|
I
I
|
i
1200
I100
I000
900
800
700
600
500
FREQUENCY (CM -~)
Fig.
1.
I.R.
spectrum
of
the
TESO.
400
Vol. 7, No. 10
CYCLIC SULPHOXIDES AS LIGANDS
TABLE l.r.
data
971
3 (cm -1)
CIO 4
Compound
5} 3
5}S = 0
THSO
1020
~)4 -
-
La(ClOt) 3
8 rMso
962
Ce(CIOI) 3
8 r.~lS 0
957
1079
620
Pr(CI04) 3
8 r,430
962
1085
620
Nd(Cl04) 3
8 fMSO
965
1075
621
Sm(Cl04) 3
8 FMSO
965
1083
620
Eu(CI04) 3
8 I'.HS 0
965
1083
621
Gd(CI04) 3
8 I')IS 0
970-960
1080
620
7.5FMSO
967
1083
620
i3y(Cl 0 4 ) 3 . 7.5TMSO
970
I081
620
I!o ( (; l OL,I )3" 7.517tlSO
967
IOR2
621
E r ( C lO,t )3 ° 7 . 5 r M S O
970
t. 0 8 2
621
Tm(CI04) 5.
? ~MSO
956
1073
620
l'b(C104)5.
7 r~iso
960
1080
621
Lu(CI04) 3.
7 rMSO
965
1085
621
Y( CIO t ) 3 . 7 . 5 I ' . q S O
970
1082
621
1'b(C104)3
7.5 I00
8.0
I0,0
9.0
MICRONS
i
I
1080
621
1:5,0
I
I
15.0 ]
20.0
I
25.0
I
80
m60 z
4o rr F--
20
Fig.2.
J
I
I
I
l
1300
1200
II00
I000
I.R.
spect.rma
of
the
l
I
900 800 FREQUENCY (CM-')
compound
of
I
I
I
700
600
500
formula
4100
Gd(CIO 4)5.8THS0.
972
CYCLIC SULPHOXIDES AS LIGANDS
Vol. 7, No. 10
REFERENCES
1 - S.K.Ramalingan (1966) 2 -
S.Soundararajan
idem.
Chem. Abstr.65,
V.N.Krishnamurthy 517
3 -
and
and
-
Curr.Sci
3308
S.Soundararajan
(India),
35,
233
(1966). -
J.inorg.nucl.Chem.,
29,
(1967).
S.K.Ramalingan
and
S.Soundararajan
-
J.inorg.nucl.Chem.,
29,
1763
(1967).
,~CKNO~LEDGEMENTS
We e x p r e s s (Fundacao support.
de
Amparo
a Pesquisa
do
Estado
our
de Sao
thanks Paulo)
to for
FAPESP financial
CYCLIC I-ADDUCTS
SULPHOXIDES
BETWEEN
AS LIGANDS.
LANTHANIDE
TETRAMETHYLENE
PERCHLORATES
Lea B . Z i n n e r
and G.¥icentini
(Received 18 J ~ e f
Departamento Instituto
AND
(T~SO).
SULPHOXIDE
.
de Qulmlca
de C u [ m i c a , U n i v e r s i d a d e
1971)
Fundamental
de Sao P a u l o , S . P a u l o ,
Brasil
INTRODUCTION
Adducts and
dimethysulphoxide
LnC15.
x DMSO
Ln(N03).
(DHSO)
(x = 3,4)
x DMSO
(3)
preparation
of
sulphoxide.
Compounds of
Pr,
Nd,
the
lanthanide
Sm, Eu~ G d ) ,
L n ( C I 0 4 ) 3. and
(1),
were
L n ( C I 0 4 ) 3. described
in
In
this
perehlorate
the
lanthanide the
y DMSO
(y = 7 , 8 )
we
Lu)
anti
the
tetramethylene
8 TblSO (Ln = L a , Dy,
were obtained. have
(2)
present
with
THSO (Ln = T b ,
in nitromethane
salts
compositions
literature.
note
L n ( C I 0 4 ) 3.
Ln(C104)3.7.5
conductances
to
adducts
composition
7 THSO (Ln = Tm, Yb,
molar
between
corresponding
Ho,
Er,
The i . r .
Ce,
Y) a n d spectra
been determined.
EXPERIMENTAL Preparation dissolved a small
of
(1:8) Inc).
volume of
chloride
adducts.
in a sufficient excess
Laboratories small
the
to
of
amount
lanthanide
of absolute
tetramethylene
The s o l i d
ethanol
constant
The h y d r a t e d
adducts
and dried
in
weight.
967
ethanol sulphoxide
were collected, vacuo
over
perchlorates and
treated
(from washed
anhydrous
were with
K and with
K a
calcium
968
CYCLIC ~JLPHOXIDES AS LIGANDS
Analytical aqueous
procedure.
solution
(Amberlite
of
IR-120
performed
The
spectrophotometer
Carbon
using
a
the ions
determined cationic
liberated
were
and hydrogen
Nujol
mulls
for
resin acid
standard
by
the usual
microanalyses
a
were
Laboratorium.
Perkin-Elmer
the
an
column
with
determined
MikroanaIytisches
with
by p a s s i n g
adducts
and a
25,00
~ 0~020C
~lodel
557
film
for
KBr p l a t e s .
Condutance
measurements.
Industrial
Instrument
and Northrup
titrating
were determined
ligand~between
were
compound through
Bernhardt
These
ions
lanthanide
method.
by A l f r e d
I~r.spectra.
the
the
II +) a n d
sodium hydroxide. oxalate-oxide
Perchlorate
VoL 7. No. 10
cell
These
w e r e made a t
~ l o d e l RC-16B c o n d u c t i v i t y
(K c = 0 , 1 0 7 0 8
bridge,
with
an
using
a Leeds
of
adducts
analytical
data.The
cm-1).
I~ESULTS :~ND DISCUSSION
Three were
obtained.
Table
compounds are benzene,
slightly
and quite
that
all
in acetone
adducts
Infrared
spectra,
to
frequencies
lower
;ind a s t r o n g ) J that is
not
bonded
composition li~and ions.
spectrum
of
is
The d a t a 1:3
the
to
tile
presented
i n an
.qhift
of
intermediary the
i.r.
the
and
Figure
of
( 50 c m - l ) .
ion.
the
chloroform
2
indicate
S--O s t r e t c h i n g
The v e r y
ion are and
that
position data
in Table
the
2 a typical
of
spectrum
3
band
indicating ion
compounds of
two
Figure
mode
perchlorate
one molecule
between
obtained,
strong,}
observed,
that
Tile e x i s t e n c e
T~ISO i n d i c a t e
3 contains li~and
and
and
in nitromethane.
perchlorate
lanthanide
Ln(Cl04)5.7.5
tetrachloride
nitrobenzene
electrolytes
o!)served
for
the
in carbon
s y m ~ l e t r y was m a i n t a i n e d
may l i e table
are
types
and nitromethane.
h considerable
l band
tetrahedral
summary of
in methanol,
measurements.
the
a
insoluble
soluble
soluble
Conductance
1 contains
practically
different
of
the
lanthanide 1 contains of
the
an a d d u c t .
12,20
12,83
15,08
13.25
13.41
::d (C l ~) | ) 3,8T,~ISO
Tb(C104)5.7.5fHS0
Dy(CI04 ) 3 , 7 . 5 T M S 0
lto (C104 ) 5,7,5T,~ISO
Er(CIO4)3.7.5TMSO
Y(C104)5,7,5L~ISO
7.60
14.55
11,84
E u ( C I 0 4 )3.8T~130
Lu (C104)3.7TMSO
II ,73
Sm(C104) 3.8T~ISO
14.12
11.30
Nd( (" 104 ) 3.81'tqS0
14.41
11.07
Pr(CIO4)5,8IHSO
l'b (C104)3.7TMSO
11,02
Ce(C104 ) 3.87~[50
~m(CIO4)3.7rMSO
]0.93
Theor.
La (C104 ) 3,8T,~IS0
Compound
Ln
7,55
14,53
14,42
14,01
13,60
13.35
15.00
12,65
12,24
11,92
11.83
11.25
11,05
11.12
11.05
Exp.
Summary
1
25,53
24.81
24.85
24,94
23,93
23,97
24,02
24,09
23,15
23,24
25.27
25.38
23,44
25,46
23.48
Fheor.
ClO 4
25,42
2.4,62
24.37
24,76
23.95
23.94
23,96
24,06
25,10
23,34
23.28
25.37
23,42
25,20
23.50
Exp.
~nalysis
of analytical
TABLE
C
50,84
27,97
28,01
28,11
28,90
28,95
29,01
29,09
29,82
29.94
29.98
30.12
30,20
30.22
30.25
Theor.
(%)
results
50,79
28,13
28,06
28,28
28,66
29,02
29,13
29,27
29,85
30,01
29.82
50.15
50.3t
30,38
30.35
iLxp.
5,18
4,69
4,70
4,72
4,85
4.86
4,87
4.88
5,03
5,03
5.03
5.06
5,07
5,07
5.08
Theor.
H
5 21
4 79
4 69
4 67
1 85
4 87
4 98
4 88
4 87
4 90
5. I 0
5 .i0
5 .06
5 .19
5 .07
Exp.
z
r
o
g-
r-
q
970
CYCLIC
SULPHOXIDES
AS LIGANDS
TABLE Electrolytic
2
conductance
Compound
Concn.
V o l . 7, N o . 1 0
in nitromethane
m mole
../k.m ( m h o ,
cm 2,
La(CI04) 3. 8 THSO Ce(Cl04) 5. 8 TMSO Pr(Cl04) 3. 8 TMSO Nd(CI04) 3. 8 TMSO Sm(CI04) 3. 8 TMSO Eu(CI04) 3. 8 TMSO Gd(CI04) 3. 8 TMSO Tb(CIO4)3.7.5THSO Dy(CIO4)3.7.STMSO Ho(CIO4)3.7.5THSO
0,99
220
0,82
222
0,96
224
0,91
215
0 89
228
0 96
221
88
222
Er(CIO4)3.7,5THSO
0
0 96
225
0 92
230
0 90
248
0 93
226
? TNSO
1
22
227
Yb(CI04)3.
7 ~MSO
0 93
230
Lu(CI04)5.
7 EHSO
0 99
225
1 07
223
Tm(CI04) 3.
Y(ClO4)s.7,5THSO
75 I00
8.0
90
'
'
I0,0
MICRONS
13.0
15.0
mo1-1)
20,0
25.0
80 A
uJ 60 Z I,.-
I-40I,-
2O
0
l
I
|
|
|
I
I
|
i
1200
I100
I000
900
800
700
600
500
FREQUENCY (CM -~)
Fig.
1.
I.R.
spectrum
of
the
TESO.
400
Vol. 7, No. 10
CYCLIC SULPHOXIDES AS LIGANDS
TABLE l.r.
data
971
3 (cm -1)
CIO 4
Compound
5} 3
5}S = 0
THSO
1020
~)4 -
-
La(ClOt) 3
8 rMso
962
Ce(CIOI) 3
8 r.~lS 0
957
1079
620
Pr(CI04) 3
8 r,430
962
1085
620
Nd(Cl04) 3
8 fMSO
965
1075
621
Sm(Cl04) 3
8 FMSO
965
1083
620
Eu(CI04) 3
8 I'.HS 0
965
1083
621
Gd(CI04) 3
8 I')IS 0
970-960
1080
620
7.5FMSO
967
1083
620
i3y(Cl 0 4 ) 3 . 7.5TMSO
970
I081
620
I!o ( (; l OL,I )3" 7.517tlSO
967
IOR2
621
E r ( C lO,t )3 ° 7 . 5 r M S O
970
t. 0 8 2
621
Tm(CI04) 5.
? ~MSO
956
1073
620
l'b(C104)5.
7 r~iso
960
1080
621
Lu(CI04) 3.
7 rMSO
965
1085
621
Y( CIO t ) 3 . 7 . 5 I ' . q S O
970
1082
621
1'b(C104)3
7.5 I00
8.0
I0,0
9.0
MICRONS
i
I
1080
621
1:5,0
I
I
15.0 ]
20.0
I
25.0
I
80
m60 z
4o rr F--
20
Fig.2.
J
I
I
I
l
1300
1200
II00
I000
I.R.
spect.rma
of
the
l
I
900 800 FREQUENCY (CM-')
compound
of
I
I
I
700
600
500
formula
4100
Gd(CIO 4)5.8THS0.
972
CYCLIC SULPHOXIDES AS LIGANDS
Vol. 7, No. 10
REFERENCES
1 - S.K.Ramalingan (1966) 2 -
S.Soundararajan
idem.
Chem. Abstr.65,
V.N.Krishnamurthy 517
3 -
and
and
-
Curr.Sci
3308
S.Soundararajan
(India),
35,
233
(1966). -
J.inorg.nucl.Chem.,
29,
(1967).
S.K.Ramalingan
and
S.Soundararajan
-
J.inorg.nucl.Chem.,
29,
1763
(1967).
,~CKNO~LEDGEMENTS
We e x p r e s s (Fundacao support.
de
Amparo
a Pesquisa
do
Estado
our
de Sao
thanks Paulo)
to for
FAPESP financial