Novel 2-hydroxyethyl substituted N-coordinate-Pd(II)(NHC) and bis(NHC)Pd(II) complexes: Synthesis, characterization and the catalytic activity in the direct arylation reaction

Article abstract of DOI:10.1007/s12039-019-1657-y

Abstract: The direct arylation reaction has attracted attention in recent years especially because of its environment-friendly properties. In this study, we researched the synthesis of 2-hydroxyethyl substituted bis(NHC)Pd(II) complexes and also the synth

Full text of DOI:10.1007/s12039-019-1657-y

J. Chem. Sci.
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6
m
m-
g
1
)
.
M
.
p
.
:
2
3
6
–
2
3
8
2
-
1
1
1
1
2
1
.
9
–
1
2
2
3
2
.
5
–
1
2
2
.
7
–
1
2
4
.
4
–
1
2
4
.
8
–
1
2
6
.
6
–
1
2
6
.
7
–
1
1
2
6
4
.
9
–
1
2
3
7
.
1
–
°
C
C
;
m
1
3
9
9
m
;
m
4
2
3
c
.
A
n
a
l
.
C
a
l
c
.
f
o
r
(
C
N
)
(
O
-
H
)
2
8
.
2
–
1
8
.
3
–
1
2
8
.
7
–
1
3
0
.
9
–
1
3
1
.
0
–
1
3
1
.
3
–
1
3
4
.
1
–
3
.
2
–
1
4
.
8
–
H
C
l
N
O
P
d
:
C
:
5
9
.
5
7
H
N
:
5
.
7
9
;
N
:
7
.
3
1
.
F
o
u
n
d
:
C
:
3
8
4
4
2
4
2
1
3
6
.
2
–
1
6
.
9
a
n
d
1
3
7
.
1
.
(
A
r
-
C
)
;
1
8
9
.
8
a
n
d
1
9
0
.
0
(
2
-
C
-
P
d
)
.
5
1
2
4
9
.
6
3
;
H
:
5
.
8
2
;
N
:
7
.
3
6
.
H
M
R
(
4 0
O H
0
M
;
H
z
, C DC I ) ; d
3
.
7
6
2
,
a
n
d
2
.
5
9
(
s
,
2
H
,
–
N
C
H
C
2
H
)
2
.
2
5
–
2
.
2
9
a
n
d
2
.
3
–
–
2
.
3
9
(
2C
s
,
9
H
,
–
N
C
H
C
H
(
C H3) ) ;
3
4 .
, J
0
2
a
n
d
4
.
2
8
(
m
H z –
,
2
6
2
2 . 1 f Synthesis of cis/trans-dichlorobis[1-(2-hydrox-
yethyl)-3-(3-methylbenzyl)benzimidazol-2-ylidene]palla-
dium(II), 2d
p
b
H
N
C
H
H
O
H
)
;
5
.
1
0
a
n
d
5
.
1
8
4
(
t
,
4
H
=
6
a
n
d
6
2
N
C
H
C
H
O
H
)
;
5
.
2
9
a
n d
- H
5
.
3
2
3
(
s
,
H
,
–
N
C
H 2
C
H
( C H ) ) ;
2 3 3
2
2
6
:
T
h
i
s
c o
r 1a
m
p
o
u
n
d
w
a
s
p
r
e
p
a
r
e
x 2d
d
w
i
t
h
t
h
e
s
a
m
e
1
6
2
.
3
3
–
7
2
.
3
9
(
m
,
1
2
H
,
A
r
)
.
C
N
M
(C
R
(
1
)
0
0
M
H
z
,
C
D
C
I
3
)
;
d
r
o
c
e
d
u
r
e
a
s
t
h
a
t
1
h
f
o
.
B
u
t
t
h
e
c
l
o
m
p
l
e
w
a
s
p
r
e
p
a
r
e
d
0
.
9
–
1
.
0
a
n
d
2
2
.
3
(
–
N
C
H
C
H
H
)
;
3
0
.
4
a
n
d
3
4
.
1
(
–
2
–
2
6
2
3
3
y
u
s
i
n
g
-
(
2
-
h
y
d
r
o
x
y
e
t
h
y
)
-
3
-
(
3
-
m
e
t
h
y
l
b
e
i
n
z
y
l
)
b
e
n
-
f
N
C
H
C
H
O
H
)
;
4
9 .
H C
6
a
n
d
5
0
.
2
(
–
N
C
H
C
H
(
C H ) ) ;
3 3
6
2
1
.
2
2
2
6
4
z
i
m
i
d
a
z
o
l
i
u
m
c
l
o
r
i
d
e
(
1
5
1
m
g
.
0
.
5
0
m
m
o
l
)
n
s
t
e
a
d
o
a
1
1
1
n
d
6
1
.
5
(
–
N
C
H
O H
2
)
;
1
1
0
.
2
–
1
1
0
.
4
–
1
1
1
.
3
–
1
1
.
5
2
1
-
(
2
-
h
y
d
r
o
x
y
e
t
h
y
l
)
-
3
-
m
e
t
h
y
l
b
e
n
z
i
m
i
d
a
z
o
l
i
u
m
c
h
l
o
r
i
d
e
.
1
1
.
9
–
1
2
2
.
8
–
1
2
3
.
0
–
1
2
3
.
3
–
1
2
3
.
7
–
1
2
7
.
5
–
1
2
8
.
0
–
1
2
8
.
1
–
1
2
8
.
3
–
Y
i
e
l
d
1
:
7
4
%
(
1
3
1
m
g
)
.
M
.
p
.
1
7
5
–
1
7
6 °
n
C
;
m
:
)
1
4
1
f o r
0
(
C
N
1
m -
;
m( O
:
3
4
0
4
c
m -
.
A
a
l
.
C
a
l
c
.
2
8
.
5
–
1
3
4
.
2
–
1
3
4
.
5
–
1
3
4
.
7
–
1
3
8
.
4
a
n
d
1
3
8
.
5
.
(
A
r
-
C
)
;
1
8
0
.
9
a
n
d
c
-
H
)
8
2
.
3
(
2
-
C
-
P
d
)
.
C
H
C
l
N
O
P
d
:
C
:
5
7
.
5
1
2
;
H
:
5
.
1
1
;
N
0
:
7
.
8
9
.
F
o
u
n d : C :
I
3
4
3
6
2
4
2
5
1
–
5
–
7
.
5
6
;
H
d
:
5
.
1
4
;
N
:
7
.
9
2
.
H
N
M
R
(
4
0
M
H
z
,
C
D
9
C
)
;
d
3
.
6
5
a
n
2
.
6
0
(
s
,
C H3
2
H
,
–
N
C
H
C
H
OH
2
)
;
2
.
5
5
a
n
d
2
H 2
.
5
(
s
,
6
H
,
2
2 i Synthesis of cis/trans-dichlorobis[1-(2-hydrox
yethyl)-3-(2,3,4,5,6-pentamethylbenzyl)benzimidazol-
.
1
N
C
H
(
2
C
H
)
)
;
3
.
4
7
a
n
d
3
.
8
CH2
2
(
m
,
4
H
,
–
N
C
C H O H
2
)
;
6
4
.
1
7
a
n
d
2C
5
.
2
9
(
(
s
,
4
H
,
–
N
C
H
O
H
)
;
5
.
8
3
a
n
- H
d
6
.
.
3
2
(
s
,
4
H
,
2
2-ylidene]palladium(II), 2g
p
:
T
g
h
i
s
t
c
o
m
p
o
r 1a
r
u
n
d
w
a
s
1
3
N
C
H
H
C H ) ) ;
3
6
.
9
3
–
7
.
6
6
(
m
2
,
1
6
H
,
A
r
)
C
N
M
R
6
4
r
e
p
a
r
e
d
x 2g
w
i
t
h
t
h
e
s
a
m
e
r
p
r
o
c
e
d
u
r
e
a
s
h
a
t
f
o
.
B
u
t
t
h
e
(
1
0
0
M
H
z
,
C
D
C
I
)
;
d
1
9
.
8
a
n
d
2
.
3
(
–
N
C
H
(
C
H
4
)
C
H
)
;
3
2
6
3
c
o
m
p
l
e
w
a
s
p
r
e
p
a
e
d
b
y
u
s
i
n
1
-
(
2
-
h
y
d
o
x
y
y
e
t
h
y
l
)
-
3
-
3
1
.
6
a
n
d
3
4
.
1
(
–
N
C
H
C
H
O
N
H
) 4
H C
;
7
.
8
a
n
d
5
0 . 4 ( – N C H
2
2
2
(
(
2
1
,
3
,
4
,
5
,
6
-
p
e
n
t
a
m
e
t
h
y
l
b
e
n
z
y
l
)
b
e
n
z
i
m
f
i
d
a
z
o
l
i
u
m
c o
e t hy l ) -3 -
h
l
r
i
d
e
(
C
H
)
;
6
0
.
6
a
n
d
6
1
.
3
(
–
C
H
O
H
)
;
1
1
1
.
3
–
1
1
2
.
5
–
6
5
2
2
8
0
m
g
.
0
.
5
0
m
m
o
l
)
i
n
s
t
e
a
d
o
1
-
(
2
-
h
y
d
r
o
x
1
1
2
3
.
4
–
1
2
3
.
5
–
1
2
6
.
6
–
1
2
6
.
9
–
1
2
7
.
8
–
1
2
7
.
9
–
1
2
3
8
.
1
–
1
2
8
.
3
–
1
2
8
.
8
–
m
e
t
h
y
l
b
e
n
z
i
m
i
d
a
z
o
l
i
u
m
c
h
l
o
r
i
d
e
.
Y
i
1
e
l
d
:
7
1
%
(
1
4
5
m
g
)
.
.
-
.
4
–
1
3
0
3
.
3
3
.
3
.
6
1
3
5
.
5
.
M
.
p
.
:
2
4
5
–
2
4
6 °
o
C
;
m
:
)
1
3
9
6
c
m
;
m
: 3
- H )
4
5
7
c
m -
1
3
0
.
7
–
1
3
1
–
1
–
1
3
4
.
4
–
1
3
4
–
1
5
.
1
a
n
d
(
C
N
(
O
(
A
r
-
C
)
;
1
8
0
.
3
a
n
d
1
8
0
.
7
(
2
-
C
-
P
d
)
.
A
n
a
l
.
C
a
l
c
.
f
r
C
H
C l N O P d
2 4 2
:
C
:
6
1
.
3 5
1
;
H
:
6
.
3
7
;
N
:
4
2
5
2
6
.
8
1
.
F
o
u
n
d
:
C
:
6
1
.
3
9
;
H
:
6
.
4
0
;
N
:
6
.
8
4
.
H
N
M
R
(
4
0
0
2
.
1
g Synthesis of cis/trans-dichlorobis[1-(2-hydrox-
yethyl)-3-(4-methylbenzyl)benzimidazol-2-ylidene]palla-
M
H
z
,
C
D
C
I
)
;
d
1
.
6
7
a
n
d
2
2
.
6
1
(
s
,
2
H
,
–
N
C
H
C H OH
2
)
;
;
3
2
2
3
4
.
1
1
–
2
.
1
3
–
2
.
2
0
–
2
.
2 3
4
a
n
d
.
2
7
(
2C
s
,
3
0
H
,
–
N
C
H
C
(
C H3
5
)
)
2
6
5
dium(II), 2e
:
s
T
h
i
s
c
o
r 1a
m
p
o
u
n
d
w
e
a
s
p
r
e
p
a
r
e
d
x 2e
w
i
t
h
t
h
e
s
a
m
e
.
7
5
, J
a
n
d
4
.
4
4
(
m
,
H
,
–
N
C
H
H
O
H
)
;
5
.
1
0
a
n
d
.
1
8
(
t
,
2
p
b
r
o
c
e
d
u
r
e
a
t
h
a
t
f
o
.
B
u
t
t
h
c
o
m
p
l
e
w
a
s
p
r
e
p
a
e
r
e
d
H
=
6
a
n
d
6
H
z
6
–
N
C
H
CH2
(
O
H
)
;
6
.
2
2
- H
a
n
d
6
.
3
2
(
s
,
4
H
,
–
0
2
7
2
1
3
y
u
s
i
n
g
1
-
(
2
-
h
y
d
r
o
x
y
e
t
h
y
l
)
-
3
-
(
4
-
m
e
t
h
y
l
b
)
e
n
z
y
l
)
b
n
z
-
f
N
C
H
2C
(
C
H ) ) ;
3 5
.
9
4
–
7
.
8
1
m
,
8
H
,
A
r
)
.
C
N
M
R
(
1
0
6
i
m
i
d
a
z
o
l
i
u
m
c
h
l
o
r
i
d
e
(
1
5
1
m
g
.
0
.
5
0
m
m
o
l
i
n
s
t
e
a
d
o
M
H
z
,
C
D
C
(C
I
)
;
d
1
6
.
5
–
1
6
.
6
–
1
6
.
8
–
1
7
.
0
–
1
7
.
1
a
n
d
1
7
.
3
1
-
(
2
-
h
y
d
r
o
x
y
e
t
h
y
l
)
-
3
-
m
e
t
h
y
l
b
e
n
z
i
m
i
d
a
z
o
l
i
u
m
c
h
l
o
r
i
d
e
.
(
–
N
C
H
C
H
)
)
;
4
9
.
( C
7
a
n
d
5
0
.
0
(
–
N
C
H
C
H
O
H
)
;
6
4
.
2
6
3
5
2
2
Y
i
e
l
d
:
7
0
%
(
1
2
4
m
g
)
.
M
.
p
.
2
2
4
–
2
2
5
°
C
;
m
:
.
1
4
0
7
a
n
d
6
OH
4
.
8
(
–
N
C
H
C
H
)
)
;
6
1
.
0
a
n
d
6
1
.
2
(
–
N
C
H
(
C
N
)
2
6
3
5
2
1
1
c
m -
;
m( O
:
3
4
3
1
c
m -
.
A
n
a
l
.
C
a
l
c
f
o
r
CH
)
;
1
1
0
.
9
–
1
1
1
.
8
–
1
2
2
.
5
–
1
2
2
.
5
–
1
2
2
.
8
–
1
2
7
.
8
–
1
2
8
.
2
–
-
H
)
2
C
H
C
l
N
O
P
d
:
C
:
5
7
.
5
2
;
H
:
5
.
1
1
;
N
0
:
7
.
8
9
.
F
o
u
n
d
:
C
:
1
1
3
2
5
.
.
5
4
–
.
1
3
2
.
7
- C
–
1
3
2
.
9
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2 1
yethyl)-3-(2,4,6-trimethylbenzyl)benzimidazol-2-ylidene]
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J. Chem. Sci.
(
2
0
1
9
)
1
3
1
:
7
8
P
a
g
e
5
o
f
1
4
7
8
Scheme 1.
S
y
n
t
h
e
s
i
s
o
f
2
-
h
y
d
r
o
x
y
e
t
h
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b
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t
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t
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N
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c
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d
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n
a
t
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P
d
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I
)
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H
C
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e
s
1
a
–
b
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c
N
o
H
m
C
p
l
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p
x
r
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s 2a–g
r
w
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n
r
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d
s
y
p
n
t
h
e
s
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z
e
d
f
r
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m
t
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a l l ad i u m a ce t at e. T h e 2 - h
e
r
e
a
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t
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f
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c
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r
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s
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d
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[
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P
l
d
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b
H
s
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w
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1
n
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n d
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t
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t
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v
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8
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l
d
d 2a– g)
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d 2a–g)
1 3
C N M R s p e c t r
o
1
Scheme 2.
i
S
y
)
n
c
t
o
h
m
e
s
p
i
s
l
o
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f
s 2a– g
2
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r
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C
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C
)
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3 . 3 Proposed catalytic cycle for N-coordinate-
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3 . 4 Direct arylation of 2-n-butylfuran and 2-n-
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m
a
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e
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t
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i
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l
e
3
)
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p
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o
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y
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m
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2
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o
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p
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h
c
o
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r
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n
m
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/
i
l
b
n
e
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e
s 1a–b
t
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)
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N
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e
C
o
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p
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f
f
s 1a–b
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w
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d
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u
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o
m
p
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w
a
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n
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t 3
s 4
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r
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d
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f
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3
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h
F
w
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4
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m
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3
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a
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C
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e
3
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C
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t 3
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r
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c
v
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s 3
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n
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m
l
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a
m
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e n
s 5
s
y
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s
l
c
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t
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t
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n
p
l
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d 6
r
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c
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m
t
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n
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n
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9
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d
6
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3
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%
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m
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9
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t
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t
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e d
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r
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n
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l
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t
h
c
6
n
%
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h
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9
9
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d
7
5
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s
s 2a–g
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t
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b
r
N
l
e
)
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e
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d
b
r
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a
t
1
e
%
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a
a
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f 2a–g
3
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C
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r
s
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o
n
s
s 1a–b
t
h
W
a
h
n
e
t
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h
e N
e
-
c
o
r
d
H
i
n
a
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t
P
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d
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I
)
(
H
o
f
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r
m
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s
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t
h
p
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t
s
5
w
9
e
r
n
a
l
y
z
6
e
6
,
9
l
e
.
a
t
h
b
i
s
(
N
C
e
I
I
)
c
o
m
p
l
e
c
s
2
a
–
c
o
n
v
i
o
w
r
e
s
r e s p e ct i v e l y ( T a b l e 4 ) . W h e n t h e N- c o o r d i n a t e -
e
v
e
d
t
7
–
9
%
n
d
3
%
g
r
e
u
s
e
d
s
t
h
e
c
a
t
a
l
y
,
t
h
s
i
e
d
p
r
o
d
u
w
a
s

J. Chem. Sci.
Table 3.
(
2
0
1
9
)
1
n
3
1
:
7
8
P
a
g
e
e
9
o
f
1
4
7
8
N
-
c
o
o
r
o
d
f
i
2
a
t
e
b
-
u
P
t
d
y
(
I
u
I
)
r
(
a
N
n
H
b
C
y
)
u
c
o
n
m
g
p
a
l
r
e
y
x
l
e
b
s
( 1a–b
o
)
a
n
d
b
i
s
(
N
H
C
)
P
d
(
I
I
)
c
o
m
p
l
e
x
s
(
2
a
–
g
)
c
a
t
a
l
y
z
e
d
d
i
r
e
c
t
a
r
y
l
a
t
i
o
n
-
n
-
l
f
s
i
r
m
i
d
e
s
.
Reaction conditions:
2
- n
)
-
P
k
b
d
e
u
(
d
t
I
y
I
b
l
)
f
c
y
u
o
r
a
m
n
p
C
(
2
x
n
m
m
o
l
)
,
( 2a–g
a
)
c
r
(
o
y
0
n
l
.
v
b
r
o
m
i
m
m
i
d
o
s
e
l
w
(
1
K
r
m
m
c
o
l
(
)
1
l
, N
m
-
m
c
o
o
c
o
r
,
o
d
D
r
i
n
M
d
a
t
A
g
e
-
c
P
(
d
2
(
I
m
r
I
)
(
L
l
N
H
1
C
3
m
)
0 °
c
C
o
m
-
p
l
,
e
x
e
s
( 1a–b
p
)
o
r
b
i
s
(
N
s
H
C
l
e
e
s
3
%
)
,
O
A
l
)
)
,
,
1
h
p
r
o
d
u
c
t
u
r
i
t
y
w
a
c
h
e
c
G
a
d
N
M
R
,
e
r
s
o
n
e
e
c
a
l
c
u
a
t
e
d
a
c
i
n
t
o
a
y
b
r
o
i
d
e
.
P
d
t
o
h
e
y
t
t
t
(
t
n
I
e
I
r
o
n
a
t
l
)
(
c
N
o
4
h
H
C
e
)
r
c
o
o
o
m
p
l
w
t
)
e
o
e
e
o
P
n
f
a
a
x
r
p
d
e
e
h
(
c
4
s 1a–b
o
a
r
d
n
l
e
u
s
e
d
e
-
a
a
s
t
h
l
l
a
e
a
t
r
c
a
t
n
p
a
l
r
y
e
e
d
s
a
n
t
c
e
a
s
-
,
l
s
e
g
b
v
o
h
x
r
w
e
r
i
t
t
n
h
s
t
h
e
a
e
e
H
r
y
e
l
l
c
a
e
o
i
t
c
n
n
i
o
n
o
e
p
n
r
-
i
o
w
o
p
x
i
t
d
i
n
u
c
d
t
a
t
s
r
a
p
(
T
i
t
s
a
n
h
b
g
e
l
e
4
)
o
c
T
.
u
T
p
h
(
n
l
i
c
i
e
-
-
e
g
o
g
s
C
d
e
r
O
n
e
C
a
s
u
H
l
t
s
)
b
e
n
v
s
i
n
s
b
t
a
i
n
e
i
n
t
h
r
y
t
i
o
o
w
a
t
t
h
t
r
t
h
a
w
g
r
3
t i
W
f
-
b
r
o
m
a
c
e
e
n
o
n
e
a
p
d
e
n
e
2
x
- n b
s 2a–g
e
p
t
o
u
t
y
h
i
o
u
d
n
e
i
h
s
i
.
h
i
b
p
i
h
O
)
i
g
h
r
v
r
s
s
h
n
o
e
n
o
l
e
t
r
o
o
4
e
t
T
c
e
i
n g
h e
e
c
a
t
a
o
e
s
r
b
i
s
,
(
N
H
C
I
I
)
c
o
m
e
e
e
n
s
e
-
s
-
e
o
u
(
-
C
d
)
t
h
p
e
a
r
s 2a–g
i
t
i
o
(
a
b
)
.
3
t
h
t
i
l
y
t
s
e
x
c
e
n
(
e
l
l
t
o
n
v
e
r
s
i
o
s
w
r
h
h
a
e
o
b
n
t
a
i
n
e
t
h
i
s
(
N
H
C
P
(
I
I
h
r
) c
e N
a
2
o
m
c
- n
b
l
e
e
s
h
I
h
w
w
e
d
h
h
m
h
r
p
r
o
x
o
n
e
n -
-
s
a
r
l
y
a
y
n
e
a
c
t
i
o
-
b
r
o
m
o
a
B
c
u
t
o
e
n
o
e
c
l h
d 2a–g
a
d
2
-
n
n
e
r
s
i
o
n
I
n
d
s
n
s
t
h
a
e
h
T
n
n
a
a
t
e
n
b
-
o
-
u
o
r
d
u
l
n
y
i
a
t
u
p
e
r
h
-
a
e
P
n
n
d
e
e
(
I
)
(
N
H
C
)
l
b
o
b
u
b
u
t
h
i
o
p
h
e
o
e
n
m
n
e
T
r
r
b
c
l
e
4
)
.
t
,
e
o
e
n
v
r
s
i
o
1a–b
v
b
.
g
t
(
l
-n
,
2
-
,
b
l
f
x
i
b
i
t
e
d
h
e
c
i
n
e
d
f
r
t
h
e
t
i
o
n
o
f
4
-
b
r n
s 1a–b
o
m
i
s
o
n
w
t
2
- n
a
e
r
r
s
i
o
t
y
t
h
o
i
t
h
t
h
e
s
a
m
e
a
r
y
l
l
t
h
i
o
p
h
e
f
o
a
l
l
c
o
m
p
l
e
x
e
a
r
o
m
i
e
l
e
3
4
)
.

7
8
P
a
g
e
1
0
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f
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4
J. Chem. Sci.
(
2
0
1
9
)
1
3
1
:
7
8
Table 4.
d
N
-
o
c
n
o
o
o
r
f
d
2
i
n
- n
a
t
-
e
b
-
u
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t
d
y
(
I
h
I
)
i
(
o
N
H
e
C
n
)
e
c
b
o
y
m
u
p
l
n
e
x
g
e
a
s
r
( 1a–b
l
)
m
a
n
e
d
s
b
i
s
(
N
H
C
)
P
d
(
I
I
)
c
o
m
p
l
e
x
e
s
(
2
a
–
g
)
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a
t
a
l
y
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r
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t
a
r
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l
a
t
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s
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r
o
i
d
.
Reaction conditions
:
b
2
- n
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s
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H
c
b
C
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y
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l
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d
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m
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x
d
m
m
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l
)
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r
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y
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b
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n
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m
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m
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l
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b
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b
m
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C
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t
d
6 8
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l
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5
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d
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s
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I
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C
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J. Chem. Sci.
(
2
0
1
9
)
1
n
3
1
:
7
8
P
a
g
e
1
1
o
d
f
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4
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7
8
Table 5.
- n
N
-
c
o
o
a
r
n
d
b
i
a
t
e
-
n
P
g
d
(
a
I
r
I
y
)
l
(
N
c
H
C
)
i
c
o
s
m
.
p
l
e
x
1
b
a
n
d
b
i
s
(
N
H
C
)
P
d
(
I
I
)
c
o
m
p
l
e
x
2
e
c
a
t
a
l
y
z
e
d
i
r
c
t
a
r
y
l
a
t
i
o
n
o
f
2
-
b
u
t
y
l
f
u
r
y
u
s
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h
l
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r
d
e
Reaction conditions
( 1b
:
2
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b
m
a
u
p
n
t
l
d
y
l
f
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r
a
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n
)
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(
,
2
0
c
m
m
o
m
l
)
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,
a
r
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,
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l
b
r
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A
m
c
i
d
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e
1
u
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m
1
m
m
o
,
c
l
D
c
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M
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c
g
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o
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t
r
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d
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m
a
n
a
L
y
t
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e
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d
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I
)
C
(
N
,
.
H
C
h
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o
r
m
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p
d
l ex
u
)
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r
b
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s
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N
H
C
)
P
d
(
I
I
)
c
o
e
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3
%
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l
K
O
m
o
l
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3
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1
6
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c
t
p
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r
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t
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s
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c
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l
c
l
a
t
e
d
a
o
r
d
i
r
c
h
l
o
r
i
d
e
Table 6.
- n
N
-
h
c
i
o
o
o
p
r
h
d
e
i
n
n
e
a
t
b
e
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s
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i
I
n
I
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(
N
H
y
C
l
)
c
c
o
o
m
p
e
l
e
s
x 1b
.
a
n
d
b
i
s
(
N
H
C
)
P
d
(
I
I
)
c
o
m
p
l
e
x
2
e
c
a
t
a
l
y
z
e
d
d
i
r
e
c
t
a
r
y
l
a
t
i
o
n
o
f
2
-
b
u
t
y
l
t
a
r
h
l
r
i
d
Reaction conditions:
( 1b
2
-
n
-
b
d
b
u
t
I
y
)
G
l
t
c
C
h
o
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n
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N
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R
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)
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m
o
l
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m
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l
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r
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a
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I
)
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N
H
C
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C
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8
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J. Chem. Sci.
Compliance with ethical standards
Conflicts of interest
(
2
0
1
9
)
1
3
1
:
7
8
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p
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References
l
o
r
n
a
t
e
s
u
t
r
a
t
e
a
e
r
e
i
t
a
s
b
e
e
c
e
v
m
r
h
s
o
a
e
r
o
n
o
u
n
c
d
i
f
f
e
r
- n
n
-
T
e
c
b
h
c
r
i
t
u
e
a
h
s
e
n
e
t
a
h
a
r
l
a
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y
o
¨
1
.
(
a
)
W
a
n
z
l
i
c
k
H
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W
a
n
d
S
c
h
o
n
h
e
r
r
H
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s y n t h e s i s o f a m e r c u r y s a l t - c a r b e n e c o m p le x Angew.
J
1
9
6
8
D
i
r
e
c
t
t
i
o
n
e
c
p
t
i
n
i
n
v
o
m
l
v
n
g
2
t
l
f
r
t
t
n
d
u
d
- n
m
d
t
¨
Chem. Int. Ed. Engl. 7 1 4 1 ; ( b ) O f e l e K 1 9 6 8 1 ,3 -
b
p
u
t
y
l
e
n
N
t
i
h
c
C
o
a
o
)
h
e
n
e
c
o
p
h
u
n
d
c
s
s
s
.
y
n
s
s
i
z
e
c
o
D
i
m
e
t
h
y
l
-
4
-
i
m
b
i
d
a
a
z
o
l
i
n
y
l
i
d
e
n
-
-
c
(
2
)
b
-
p
e
-
n
k
t
a
c
a
r
b
e
o
n
x J. Orga-
y
l
c
h
r
o
m
l
e
x
e
(
v
e
b
e
e
d
)
n
h
i
g
y
a
t
i
v
t
l
y
i
n
o
r
t
s
e
t
u
¨
e
nomet. Chem. 12
i
n
n
e
u
e
r
U
e
r
g
n
g
s
m
e
t
a
l
l
a
r
e
n
o
m
p
l
w
h
m
p
a
r
e
t
o
m
t
h
e
i
m
i
l
a
t
u
d
4
i
3
e
,
s
5
r
e
l
a
d
4
2
5
–
6
2
b
i
s
H
P
d
(
I
I
c
o
p
l
e
x
e
p
u
b
l
s
h
d
.
2
.
.
A
r
d
b
h
t
u
e
n
c
g
r
E
o
I
t
n
I
a
I
J
,
H
a
r
l
o
w
n
R
L
a
n
d
K
e J. Am. Chem. Soc. 113
i
l
n
e
M
1
9
9
1
A
s
t
a
l
e
y
s
l
l
i
n
e
c
a
r
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b
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3
6
1
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3
H
a
n
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F
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a
a
d
d
J
a
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k
M
C
2
0
0
8
H
m
e
i
t
s
e
t
r
o
c
y
c
y Angew. Chem.
l
i
c
c
a
r
b
e
n
s
:
s
y
s
i
s
n
c
o
o
r
d
i
n
a
t
i
o
n
c
h
e
r
4. Conclusions
Int. Ed. 47 3 1 2 2
L
4
.
.
a
z
r
e
g
F
,
N
a
h
r
a
F
a
n
i
h
f
d
C
a
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n
C
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