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Syntheses and chemicophysical properties of macrocyclic compounds containing a ruthenocene unit
1992
0
OLi
n-BuLi
Se L__s
aqueous
ethanol
using
high dilution
tetraoxa[16]ruthenocenophane same manner,
the reaction
conditions
(lOa) as pale
SH
Ru
to give 1,16-dithia-4,7,10,13-
yellow
of 8 with the dihalide
1,13-dithia-4,7,10-trioxa[l3]ruthenocenophane ruthenocenophane new compounds analyses,
(6, 7, and lOa-c) mass,
(9b) and
Ru
------+
9a:n=4 b: n=3 C : n=2 ability
was measured
of the
elemental
of lOa-c with
relatively
alkali,
with
alkaline-earth and transition metal 7 It was found that lOa-c showed
method. alkali
high extraction
and alkaine-earth
ability
metal
with transition
cations,
metal
while
cations.
For
extraction ability ( 99%), compared with 4a However, lOa-c showed the corresponding dithiaoxa[n]ferrocenophanes. 2+ ; 10a selectivity toward Hg2+ and Tl+ [lob (95%), 1Oc (95%) and 10a (30%) for Hg
a silver
cation,
(87%), lob supported
lOa-c
ability
0
10a : n =4 b:n=3 C :n=2
by the Pedersen's
or no extraction
showed
The structures
respectively.
OS? Br
8
The extraction
In the
(9c) also gave
were determined on the basis of their 1 13 6 H-NMR and C-NMR spectra.
Ru
cations
in 17% yield.
(lob) and l,lO-dithia-3,7-dioxa[lO]-
(10~) in 48 and 23% yield,
IR, electronic,
crystals
CL3kl
they
0
5
4
little
LiAlH&
,S
Li
&
&
Qs\ Ru
(33%), 10~
have an excellent
(2%) for Tl+].
by the electronic
(10 nm) and a decreased spin-allowed to lOa-c nitrates.
spectral
absorbance
d-d transition
in aqueous
band)
methanol
The electronic
isolated.
These
were
spectral
changes
showed
results
a hypsochromic
in the absorption
peak
on complexing
were shift
at 320 nm
of silver
are similar
and AgN03, melting
to those 4
(a
nitrate
but not in the case of alkali
(3a) with metal
higher
that these
For example,
observed
(H20:MeOH=l:l),
of 10 with HgC12
complexes
study. (15-19%)
a
of l,n-dithiaoxa[n]ferrocenophanes The complexes
It is noteworthy
metal
of the complexing
nitrates.
(lla) and points
(lib), respectively,
were
than the metal-free
Their lignads (lOa-c) and were confirmed by microanalysis to be 1:l complexes. 1 H-NMR and electronic spectra provided further information about the structure 1 H-NMR spectrum (CD3CN) of lla, the signals of of the complex (lla). In the
1993
methylene protons only
protons
next to a sulfur
of ruthenocene
+0.19,
+0.03,
nucleus
xn
lla:n=4, llb:n=3,
were
a-,
On the other
spectrum
of the complex
a signal
at 6 5.31 corresponding
(12) ' in CD CN shows 3 to the Cp ring protons.
shift of the Cp ring protons
X=Clz
compared
those
M=Ag+ X= NO,
difference
of 4, is about
in the chemical
(lOa) and the complex
those
the 'H-NMR
hand,
M=lig2+
complexation
downfield with
Cp2Ru.HgCl2
The downfield with
and B-ring
shifted
and -0.03 ppm, compared
of lOa, respectively. &7s"2
atom,
shifts
between
(lla) seems
of Hg2+ cation
of 12, Hence,
+0.7 ppm.
the
the free ligand
to be attributable
into the crown
ether
to
part
of the incorpoof the ligand, although a possibility of the direct coordination 2+ The above to the Ru atom of ruthenocene nucleus cannot be ruled out. rated Hg explanation
was supported
by the electronic
spectral
The complex
study.
lla in
acetonitrile exhibits no charge-transfer absorption of the type Cp2Ru-_)HgC12 at 9 although the absorption band at 320 nm showed a hypsochromic shift (10 280 nm, nm) and a decrease Further
of its absorbance
studies
(4%).
on the synthesis
of the related
ruthenocenophanes
are in
progress.
References 1.
c. J. Pedersen,
2.
R. E. Izatt
and J. J. Christensen,
Compounds,"
Academic
3.
G. Oepen
Sot., Chem. 767
4. 5.
a)
Comm.,
S. Ebine,
H. Watanabe,
s. Akabori,
H. Fukuda,
S. Akabori, Jpn., 56,
Multidentate
Macrocyclic
Ann. Chem.,
1979,
(1980).
1094.
J. F. Biernat
A. P. Bell and D. Hall,
and A. Ratajczak,
P. D. Beer,
Polish
and C. D. Hall,
and J. Chem.
J. Chem.,
J. Chem.
Sot.,
1161.
b) M. Sato,
1393.
(1967).
(1977).
B. Czech
163.
2495
"Synthetic
36, 2521
P. J. Hammond,
1983,
M. Sato, M. Kubo,
Sot.
Liebigs
1980,
and footnotes
Sot., E,
New York
Tetrahedron,
(1980).
Comm.,
Chem.
Chem.
Press,
and F. Vagtle,
T. Wilczewski,
2,
J. Amer.
537
S. Ebine, Y. Habata,
Y. Habata, (1983).
ibid.,
56,
1459
ibid.,
57,
63 (1984).
and S. Akabori,
(1983).
Tetrahedron
and S. Akabori, M. Sato,
Y. Sakamoto,
S. Akabori,
S. Akabori, S. Akabori,
Chem.
and S. Ebine, M. Sato,
Y. Habata,
S. Shibahara,
Y. Habata,
Lett, Lett., Chem.
1982, 1982,
1982, -Bull. Chem.
and S. Ebine,
Y. Habata,
and M. Sato,
1753.
Lett.,
and S. Ebine, M. Sato,
185.
and M. Sato,
ibid.,
57, 68 --
(1984). 6.
All new compounds
gave
Selected
and spectral
physical
6: m.p.
183.5-184.0°C,
(CDC13)
6 4.48
7: m.p.
116.8-117.8'C,
(m, 4H),
satisfactory
MS
4.87 MS
data
(m/e) 326
elemental
analyses
for 6, 7, lOa-c,
and spectral
and lla-b
(M++l, 20%) and 325
data.
are as follows.
(M+, lOO%),
'H-NMR
(m, 4H).
(m/e) 396
(M++l, 25%) and 325
(M+, lOO%),
1
H-NMR
1994
(CDCl3)
6 2.25
Hz, H
4H).
8' 10a: m.p. (CD3CN)
(s, SH, 2H), 4.47
46.2-48.0°c,
6 4.74
Hz, OCH2CH2S,
4H).
13c-~M~
(OCH2),
70.9
(CD3CN)
(OCH2),
6 4.76
13C-NMR 70.5
(OCH2),
oCK2CH$:f 4H). C-NMR (OCH2),
4H),
39.0
and 39.6
4H), 2.83 m.p.
(t, J=1.8
3.68
7.
8.
Federation
conditions
(Solvent:
polyether:
7 x 10 -4 M .
of metal
Y. S Sohn,
(t, J=6.3
(t, J=6.3 Hz, SCH2CH20,
C. J. Pedersen,
tration
12H). !CD~CN)
(t, J=1.7
Water
(M+, lOO%),
Proceedings,
(OCH2),
(M+, loo%),
Hz, H6, 4H), (t, J=6.3
(Co), 71.5
(t, J=1.8
(CH~CN)
5 4.91
71.2
lH-NMR
3.65
(s,
Hz, SCH2CH20,
(OCH2),
70.8
1305
and dichloromethane
Hz, Ha, 4H), 4.64
4H), 3.52 310 nm
(s, 0Cfi2CH20,
(E 455).
(t, ,=1.18 Hz, H e' 4H). 4.77
Uv (CH3CN) 2,
'H-NMR
(E 472).
6 4.93
Hz, SCH2CH20,
4H).
71.3
320 nm (a 472).
(Cc), 72.0
uv
(OCH2),
(Co), 71.4
(t, J=6.0 Hz, 0CH2CH2S,
'H-NMR
(t,
4H), 3.61 (t, 8' (t, J=6.3 Hz, SCH2CH20,
8H), 2.87
(Ce), 72.3
320 nm
3.63
Hz, SCc2CH20,
320 nm (E 472).
(M++l, 23%) and 410
(CD~CN)
Hz, SCH2CH20,
71.5
'H-NMR
(t, J=1.7 HZ, H
(CH~CN)
CC,), 77.1
'H-NMR
157.0-157.5oc,
3.08
uv
UV (CH~CN)
(SCH2).
172.0-173.0°C,
(t, J=1.8 Hz, HB, 4H), 3.72 8H),
(Cb), 77.0
(m/e) 411
E 90.4
(t, J=6.3
(C&
(t, J= 6.3 Hz, SCH2Cf120, 4H), 3.14
(CD3CN):
Ha, 4H),
HZ,
2.86
(t, J=1.8
(M+, loo%),
(M++l, 25%) and 454
(t, J=1.7 Hz, Ha, 4H), 4.62 3.73
12H),
(Ca), 72.6
(s, 0CH2CH20,
(SCH2). MS
(t, J=1.7
UV (CH3CN):
(m/e) 455
6 89.2
(t, J= 1.8 Hz, Ha, 4H),
llb:
cc,), 77.3
3.59
lOl.O-101.5"C,
4H),
4.61
(s, OCH2CE20,
(SCH2).
MS
(CD~CN):
6 4.79
lla: m.p.
39.6
Hz, Ha, 4H), and 4.66
(M++l, 28%) and 498
(t, J=1.7 HZ, Ha, 4H), 4.61
4H).
(CD3CN)
F 88.1
38.5-39.2'C,
Hz, SCH2CH20,
(OCH2),
4H), 3.51
(CD~CN)
J=6.3
10~: m.p.
(m/e) 499
(t, J=1.7 HZ, He, 4H),
J=6.3
lob: m.p.
MS
(t, J=1.8
4H),
3.68
310 nm
(1968).
(1:l).
(s, 0CE2CH20,
(383). Extraction
Concentration
of
Concenof picric acid: 7 x 10 -5 M. +2 , HgC12 was used): 0.1 M.). (in the case of Hg
Concentration
nitrates
D. N. Hendrickson,
and H. B. Gray,
J. Amer.
Chem.
Sot., 93,
3603
(1971). 9.
This complex Chiorboli, (Received
was prepared
U. Mazzi, in Japan
according
to the literature:
and G. L. Zucchini,
30 January
1984)
G. Chim.
0. Traverso,
Italiana,
107,
181
C. (1977).
0
OLi
n-BuLi
Se L__s
aqueous
ethanol
using
high dilution
tetraoxa[16]ruthenocenophane same manner,
the reaction
conditions
(lOa) as pale
SH
Ru
to give 1,16-dithia-4,7,10,13-
yellow
of 8 with the dihalide
1,13-dithia-4,7,10-trioxa[l3]ruthenocenophane ruthenocenophane new compounds analyses,
(6, 7, and lOa-c) mass,
(9b) and
Ru
------+
9a:n=4 b: n=3 C : n=2 ability
was measured
of the
elemental
of lOa-c with
relatively
alkali,
with
alkaline-earth and transition metal 7 It was found that lOa-c showed
method. alkali
high extraction
and alkaine-earth
ability
metal
with transition
cations,
metal
while
cations.
For
extraction ability ( 99%), compared with 4a However, lOa-c showed the corresponding dithiaoxa[n]ferrocenophanes. 2+ ; 10a selectivity toward Hg2+ and Tl+ [lob (95%), 1Oc (95%) and 10a (30%) for Hg
a silver
cation,
(87%), lob supported
lOa-c
ability
0
10a : n =4 b:n=3 C :n=2
by the Pedersen's
or no extraction
showed
The structures
respectively.
OS? Br
8
The extraction
In the
(9c) also gave
were determined on the basis of their 1 13 6 H-NMR and C-NMR spectra.
Ru
cations
in 17% yield.
(lob) and l,lO-dithia-3,7-dioxa[lO]-
(10~) in 48 and 23% yield,
IR, electronic,
crystals
CL3kl
they
0
5
4
little
LiAlH&
,S
Li
&
&
Qs\ Ru
(33%), 10~
have an excellent
(2%) for Tl+].
by the electronic
(10 nm) and a decreased spin-allowed to lOa-c nitrates.
spectral
absorbance
d-d transition
in aqueous
band)
methanol
The electronic
isolated.
These
were
spectral
changes
showed
results
a hypsochromic
in the absorption
peak
on complexing
were shift
at 320 nm
of silver
are similar
and AgN03, melting
to those 4
(a
nitrate
but not in the case of alkali
(3a) with metal
higher
that these
For example,
observed
(H20:MeOH=l:l),
of 10 with HgC12
complexes
study. (15-19%)
a
of l,n-dithiaoxa[n]ferrocenophanes The complexes
It is noteworthy
metal
of the complexing
nitrates.
(lla) and points
(lib), respectively,
were
than the metal-free
Their lignads (lOa-c) and were confirmed by microanalysis to be 1:l complexes. 1 H-NMR and electronic spectra provided further information about the structure 1 H-NMR spectrum (CD3CN) of lla, the signals of of the complex (lla). In the
1993
methylene protons only
protons
next to a sulfur
of ruthenocene
+0.19,
+0.03,
nucleus
xn
lla:n=4, llb:n=3,
were
a-,
On the other
spectrum
of the complex
a signal
at 6 5.31 corresponding
(12) ' in CD CN shows 3 to the Cp ring protons.
shift of the Cp ring protons
X=Clz
compared
those
M=Ag+ X= NO,
difference
of 4, is about
in the chemical
(lOa) and the complex
those
the 'H-NMR
hand,
M=lig2+
complexation
downfield with
Cp2Ru.HgCl2
The downfield with
and B-ring
shifted
and -0.03 ppm, compared
of lOa, respectively. &7s"2
atom,
shifts
between
(lla) seems
of Hg2+ cation
of 12, Hence,
+0.7 ppm.
the
the free ligand
to be attributable
into the crown
ether
to
part
of the incorpoof the ligand, although a possibility of the direct coordination 2+ The above to the Ru atom of ruthenocene nucleus cannot be ruled out. rated Hg explanation
was supported
by the electronic
spectral
The complex
study.
lla in
acetonitrile exhibits no charge-transfer absorption of the type Cp2Ru-_)HgC12 at 9 although the absorption band at 320 nm showed a hypsochromic shift (10 280 nm, nm) and a decrease Further
of its absorbance
studies
(4%).
on the synthesis
of the related
ruthenocenophanes
are in
progress.
References 1.
c. J. Pedersen,
2.
R. E. Izatt
and J. J. Christensen,
Compounds,"
Academic
3.
G. Oepen
Sot., Chem. 767
4. 5.
a)
Comm.,
S. Ebine,
H. Watanabe,
s. Akabori,
H. Fukuda,
S. Akabori, Jpn., 56,
Multidentate
Macrocyclic
Ann. Chem.,
1979,
(1980).
1094.
J. F. Biernat
A. P. Bell and D. Hall,
and A. Ratajczak,
P. D. Beer,
Polish
and C. D. Hall,
and J. Chem.
J. Chem.,
J. Chem.
Sot.,
1161.
b) M. Sato,
1393.
(1967).
(1977).
B. Czech
163.
2495
"Synthetic
36, 2521
P. J. Hammond,
1983,
M. Sato, M. Kubo,
Sot.
Liebigs
1980,
and footnotes
Sot., E,
New York
Tetrahedron,
(1980).
Comm.,
Chem.
Chem.
Press,
and F. Vagtle,
T. Wilczewski,
2,
J. Amer.
537
S. Ebine, Y. Habata,
Y. Habata, (1983).
ibid.,
56,
1459
ibid.,
57,
63 (1984).
and S. Akabori,
(1983).
Tetrahedron
and S. Akabori, M. Sato,
Y. Sakamoto,
S. Akabori,
S. Akabori, S. Akabori,
Chem.
and S. Ebine, M. Sato,
Y. Habata,
S. Shibahara,
Y. Habata,
Lett, Lett., Chem.
1982, 1982,
1982, -Bull. Chem.
and S. Ebine,
Y. Habata,
and M. Sato,
1753.
Lett.,
and S. Ebine, M. Sato,
185.
and M. Sato,
ibid.,
57, 68 --
(1984). 6.
All new compounds
gave
Selected
and spectral
physical
6: m.p.
183.5-184.0°C,
(CDC13)
6 4.48
7: m.p.
116.8-117.8'C,
(m, 4H),
satisfactory
MS
4.87 MS
data
(m/e) 326
elemental
analyses
for 6, 7, lOa-c,
and spectral
and lla-b
(M++l, 20%) and 325
data.
are as follows.
(M+, lOO%),
'H-NMR
(m, 4H).
(m/e) 396
(M++l, 25%) and 325
(M+, lOO%),
1
H-NMR
1994
(CDCl3)
6 2.25
Hz, H
4H).
8' 10a: m.p. (CD3CN)
(s, SH, 2H), 4.47
46.2-48.0°c,
6 4.74
Hz, OCH2CH2S,
4H).
13c-~M~
(OCH2),
70.9
(CD3CN)
(OCH2),
6 4.76
13C-NMR 70.5
(OCH2),
oCK2CH$:f 4H). C-NMR (OCH2),
4H),
39.0
and 39.6
4H), 2.83 m.p.
(t, J=1.8
3.68
7.
8.
Federation
conditions
(Solvent:
polyether:
7 x 10 -4 M .
of metal
Y. S Sohn,
(t, J=6.3
(t, J=6.3 Hz, SCH2CH20,
C. J. Pedersen,
tration
12H). !CD~CN)
(t, J=1.7
Water
(M+, lOO%),
Proceedings,
(OCH2),
(M+, loo%),
Hz, H6, 4H), (t, J=6.3
(Co), 71.5
(t, J=1.8
(CH~CN)
5 4.91
71.2
lH-NMR
3.65
(s,
Hz, SCH2CH20,
(OCH2),
70.8
1305
and dichloromethane
Hz, Ha, 4H), 4.64
4H), 3.52 310 nm
(s, 0Cfi2CH20,
(E 455).
(t, ,=1.18 Hz, H e' 4H). 4.77
Uv (CH3CN) 2,
'H-NMR
(E 472).
6 4.93
Hz, SCH2CH20,
4H).
71.3
320 nm (a 472).
(Cc), 72.0
uv
(OCH2),
(Co), 71.4
(t, J=6.0 Hz, 0CH2CH2S,
'H-NMR
(t,
4H), 3.61 (t, 8' (t, J=6.3 Hz, SCH2CH20,
8H), 2.87
(Ce), 72.3
320 nm
3.63
Hz, SCc2CH20,
320 nm (E 472).
(M++l, 23%) and 410
(CD~CN)
Hz, SCH2CH20,
71.5
'H-NMR
(t, J=1.7 HZ, H
(CH~CN)
CC,), 77.1
'H-NMR
157.0-157.5oc,
3.08
uv
UV (CH~CN)
(SCH2).
172.0-173.0°C,
(t, J=1.8 Hz, HB, 4H), 3.72 8H),
(Cb), 77.0
(m/e) 411
E 90.4
(t, J=6.3
(C&
(t, J= 6.3 Hz, SCH2Cf120, 4H), 3.14
(CD3CN):
Ha, 4H),
HZ,
2.86
(t, J=1.8
(M+, loo%),
(M++l, 25%) and 454
(t, J=1.7 Hz, Ha, 4H), 4.62 3.73
12H),
(Ca), 72.6
(s, 0CH2CH20,
(SCH2). MS
(t, J=1.7
UV (CH3CN):
(m/e) 455
6 89.2
(t, J= 1.8 Hz, Ha, 4H),
llb:
cc,), 77.3
3.59
lOl.O-101.5"C,
4H),
4.61
(s, OCH2CE20,
(SCH2).
MS
(CD~CN):
6 4.79
lla: m.p.
39.6
Hz, Ha, 4H), and 4.66
(M++l, 28%) and 498
(t, J=1.7 HZ, Ha, 4H), 4.61
4H).
(CD3CN)
F 88.1
38.5-39.2'C,
Hz, SCH2CH20,
(OCH2),
4H), 3.51
(CD~CN)
J=6.3
10~: m.p.
(m/e) 499
(t, J=1.7 HZ, He, 4H),
J=6.3
lob: m.p.
MS
(t, J=1.8
4H),
3.68
310 nm
(1968).
(1:l).
(s, 0CE2CH20,
(383). Extraction
Concentration
of
Concenof picric acid: 7 x 10 -5 M. +2 , HgC12 was used): 0.1 M.). (in the case of Hg
Concentration
nitrates
D. N. Hendrickson,
and H. B. Gray,
J. Amer.
Chem.
Sot., 93,
3603
(1971). 9.
This complex Chiorboli, (Received
was prepared
U. Mazzi, in Japan
according
to the literature:
and G. L. Zucchini,
30 January
1984)
G. Chim.
0. Traverso,
Italiana,
107,
181
C. (1977).