786
M.G. Cowan et al.
7
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m
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(
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C o w a n , M . G . ; B r o o k e r , S . Coord. Chem. Rev. 2012, 256,
9 4 4.
H
)
,
7
.
9
5
(
m
,
2
H
,
H
)
.
6
/
9
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/
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T
.
;
T
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H
.
;
N
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a
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o
,
M
.
;
T
a
k
a
i
s
h
i
,
S
.
;
k a z a w a , Y . ; Y a m a s h i ta , M . Inorg. Chem. 2010, 49,
N
a
3 5 8.
8
(
3
)
F
N
e
a
a
r
k
k
b
a
a
i
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.
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.
;
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,
,
H
Y
.
.
;
;
Symmetric quinoxaline ligand: Hquinoxquinox
t
o
.
;
o
j
i
.
;
C
i
p
o
,
.
;
j
i
m
A
s
o
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o
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x
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d
(
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9
.
7
m
g
,
T
i
0 0 8.
s
i
,
.
Y
a
a
s
h
t
. J. Am. Chem. Soc. 2006, 128,
0
2
.
9
1
8
m
m
o
l
)
i
0 8
n
t
h
i
o
n
y
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(
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)
Z
e
b
r
e
t
,
S
.
;
D
u
p
o
n
t
,
N
.
;
J. Chem. Eur. J. 2009, 15, 3 3 5 5.
B
e
r
n
a
r
d
i
n
e
l
l
i
,
G
.
;
H
a
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.
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;
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s
p
e
n
s
i
o
n
a
s
s
.
;
K
n
i
m
a
,
,
F
. J. Am. Chem. Soc. 2005, 127
R
0
1
0 .
. Chem.
r
e
fl
u
x
e
d
a
t
1
2
C
f
o
r
2
d
a
y
s
.
M
e
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h
a
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l
(
2
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m
L
)
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(
6
)
)
P
o
i
t
i
l
a
r
t
.
;
B
e
r
n
o
t
,
Eur. J. 2007, 13, 1 6 0 2.
K
.
;
S
e
s
s
o
l
i
,
.
;
G
a
t
t
e
s
c
i
,
D
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d
,
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w
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d
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´
(
7
C
B
C
B
o
r
o
w
o
w
a
k
a
k
n
e
n
e
,
M
.
S
.
S
G
.
;
O
l
g
u
ı
n
,
J
.
;
N
a
r
a
y
a
n
. J. Am. Chem. Soc. 2012, 134
a
s
w
a
m
y
,
S
, 2 8 9 2.
.
;
T
a
l
l
o
n
,
J
.
L
.
;
p
r
e
s
s
ur
e
.
C
o
l
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m
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c
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o
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,
s
o
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2
0
:
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o
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m
(
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y
i
e
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d
e
d
(
(
1
8
9
0
)
)
)
,
M
G
.
;
B
r
o
o
k
e
r
,
S
. Chem. Soc. Rev. 2015, 44
. Dalton Trans. 2012, 41
8
a
2
.
,
1
4
6
5
.
t
h
e
p
r
o
d
u
c
t
a
s
a
n
o
f
f
-
w
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i
t
e
s
o
l
i
d
(
2
5
.
8
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,
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3
%
,
r
o
o
r
,
,
2
8
0
.
.
L
R
C
f
¼
0
.
8
)
.
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m
e
n
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a
n
a
l
y
s
i
s
c
a
l
c
d
%
)
f
o
r
(
M
New. J. Chem., 2014
S
m
M
i
l
l
e
r
,
R
.
G
.
;
N
a
r
a
y
a
n
,
n
a
r
r
J
7
a
1
s
w
m
;
y
,
S
.
;
T
a
R
,
l
l
o
n
,
J
.
a
;
B
r
o
a
o
o
s
k
w
e
e
r
,
S
.
,
,
H
N
O
6
(
3
2
9
.
H
1
3
2
)
:
C
a
l
c
.
C
6
5
.
6
5
H
N
3
M
4
.
3
7
N
2
1
.
2
7
;
9
3
M
.
i
l
l
l
e
l
r
,
.
G
.
;
N
a
r
y
a
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a
r
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y
1
8
1
1
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2
1
.
;
C
u
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a
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r
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k
r
R
,
S
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G
.
i
.
;
J
a
m
e
o
M
e
s
o
,
i
G
B
;
T
a
o
n
J
.
L
.
a
n
d
B
r
o
k
,
S
.
f
o
u
n
d
:
C
4
.
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3
.
7
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2
0
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.
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,
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p
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p
r
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r
t
,
o
n
.
C
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l
)
: d
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)
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.
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s
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/ 7
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(
1
1
1
2
)
)
l
e
r
,
.
M
;
B
r
o
k
e
S
R
. Inorg. Chem., 2015, 54
.
,
5
c
S
3
9
,
8
J
.
8
H2
.
3
7
9
-
8
2
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m
,
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/ 4 / 8 / 1 1
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,
.
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.
;
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,
.
.
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.
;
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S
o
r
u
t
h
o
.
n
J
,
;
P
D
o
.
o
;
k
P
r
i
e ;
. Inorg.
.
R
.
) .
/1 0
/
3
/
9
Y
Chem. 2014, 53
a
i
n
,
O
.
;
L
a
n
e
,
R
.
;
K
p
e
t
,
C
.
B
S
r
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r
,
,
1
2
0
6
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.
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9
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)
)
)
)
)
)
)
)
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)
C
o
w
a
2015, 44, 2 8 8 0.
n
,
M
.
G
.
;
M
i
l
l
e
r
R
.
G
.
;
B
r
o
o
k
e
r
,
.
D
a
l
t
o
n
.
T
r
a
n
s
.
[CoII(quinoxpz)2]· CH3OH
W
1993, 207
o
c
a
d
l
o
,
S
.
;
M
a
.
s
s
a
,
W
.
;
F
o
l
g
a
d
o
,
J
,
.
-
V
. Inorg. Chim. Acta.
. Inorg.
. Helv. Chim. Acta.
. J. Med. Chem.
. Acc. Chem. Res.
(
1
9
9
)
A
s
o
l
u
t
i
o
n
o
f
c
o
b
a
l
t
(
I
I
)
t
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u
n
o
r
l
o
b
o
r
a
t
e
h
e
x
a
h
y
d
d r a te
t
S
a
h
u
,
Chem. Acta. 2010, 363
R
.
;
P
a
d
h
i
,
S
.
K
.
;
J
e
n
4
a
4
,
8
H
.
S
.
;
M
a
n
i
v
a
n
n
a
n
,
V
(
2
4
.
2
m
g
,
0
.
0
7
1
1
m
m
o
l
)
i
n
m
e
H quinoxpz
t
h
a
o
(
5
m
L
)
w
a
s
a
d
e
d
o
( 1
W
)
.
v
1957, 60, 2 0 5 .
o
n
K
e
l
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e
r
-
S
c
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i
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r
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i
n
,
.
;
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r
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9 m
(
3
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.
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g
,
0
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1
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m
o
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)
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e
(
1
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,
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.
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)
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m
e
t
h
a
n
o
l
(
5
m
L
)
S
2002, 45, 5 6 0 4.
e
i
t
z
,
L
.
E
.
;
S
u
l
i
n
g
,
W
.
J
.
;
R
e
y
n
o
l
d
s
,
R
.
C
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d
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l
o
r
o
m
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t
h
a
n
e
(
m
L
)
.
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h
e
r
t
e
s
u
l
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r
e
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p
o
r
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.
J
2001, 34
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,
,
.
W
8
G
.
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.
;
F
a
r
r
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l
l
,
B
.
M
.
;
M
a
l
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,
J
.
F
T
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s
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w
,
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B
.
;
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a
r
d
i
n
g
,
C
.
J
.
;
M
c
K
e
e
,
V
.
s o n J. J. Chem. Soc., Chem. Commun. 1995, 1 0 3 5 .
;
M
o
r
g
a
n
,
G
.
G
.
;
a
s
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.
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,
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e
r
,
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.
;
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u
r
.
J
.
I
n
o
r
g
.
Chem. 2009, 2009
n
,
1
2
.
T
a
1984, 106, 2 4 4 .
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,
R
.
;
K
e
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,
.
;
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.
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.
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.
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.
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o
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.
Supplemental data
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