0.1048o
关键词
：
二茂铁二茂钛配合物异核配合物芳香酸
Study
on
Synthesis
and
Reaction
of
Hetero
Nucleus
Titanocene
Complexes
Containing
Ferroenyl
Group
in
Mild
Condition
Wang
Gaofeng
Abstract:
Titanocene
derivatives
have
received
considerable
attention
due
to
their
potential
as
highly
active
and
selective
polymerization
catalyst
precursors,
hydrogenation
and
isomerization,
anti-tumour
and
anti-oxidative
action.
In
this
dissertation,
the
syntheses
of
titanocene
derivatives
are
reviewed,
especially
in
water
or
two
phase
system.
The
syntheses
of
titanocene
complexes
containing
ferroenyl
group
were
also
reviewed.
A
series
of
ligands
and
tianocene
complexes
bearing
phenylferrocene
have
been
prepared
and
characterized.
The
main
results
of
this
dissertation
are
shown
as
follows:
1.
Dichloride
titanocene
and
dimethylcyclopentadienyl
dichlorotitanium
were
prepared
by
using
titanium
tetrachloride,
dicyclopentadiene,
and
dimethylcyclopenta
-diene
as
raw
materials.
Compounds
5-ferrocenyl-2-hydroxyIbenzoic
acid,
2-ferrocenyIbenzoic
acid
and
4-ferrocenylbenzoic
acid
were
prepared
by
using
the
following:
ferrocene,
5-aniinosaIisyIic
acid,
2-aminobenzoic
acid
and
4-aminobenzoic
acid
respectively,
4-ferrocenylbenzoic
acid
was
prepared
according
to
the
modified
procedure.
In
the
meantime,
two
alkyl
ferrocenyl
complexes,
5-ethylferrocenyl
-2-hydroxylbenzoic
acid
and
5-diethyl-
ferrocenyl-2-hydroxylbenzoic
acid
were
synthesized
by
reacting
ethylferrocene/diethylferrocene
and
5-aminosaIisylic
acid.
All
of
complexes
were
characterized
by
IR
and
*H
NMR
spectra.
2.
A
new
complex
was
prepared
by
"'one-pof
method
from
ferrocene,
phosphorus
trichloride
and
4-aminosalicylic
acid,
which
was
characterized
by
UV-vis,
elemental
analysis
IR,
*H
NMR
and
single-crystal
X-ray
analysis.
Crystallographic
characterization
of
the
new
complex
shows
that
the
crystal
is
in
the
triclinic
system,
space
group
Pl
with
a
=
5.954(2)
A,b=
13.208
(5)
A,c=
13.252(5)
A,a
=
60.993(7)
A,
p
=
84.342(8)
。
,
Y
=
86.933(8)
。
，
V
=
906.8(6)
De
=
L601
g/cm
：
Z
=
2,
g
=
0.987
mm",
F(OOO)
=
452,
R|
=
0.0647,
wR?
=
0.1333.
3.
Two
new
titanocene
complexes
containing
a
ferrocenyl
group
were
prepared
in
two-phase
media
by
the
reaction
of
titanocene
dichloride/dimethylcyclopentadienyl
dichlorotitanium
with
5-ferrocenyl-2-hydroxyI-benzoic
acid
in
the
presence
of
acetylace
-tone/5-sulfbsalicylic
acid
under
mild
conditions.
The
compounds
were
characterized
by
UV-vis,
elemental
analysis,
IR,
'H
NMR
and
X-ray
diffraction
analyses.
Based
on
the
Ill
UV-vis
spectrum
the
reaction
process
was
also
studied.
Single
X-ray
diffraction
analyses
show
that
the
conformation
of
two
cyclopentadienyl
rings
bonding
iron
change
from
eclipsed
conformer
to
staggered
conformer
while
methyl
groups
link
to
the
other
two
cyclopentadienyl
rings
of
the
molecule.
4.
Two
titanocene
complexes
containing
a
ferrocenyl
group
were
characterized
by
X-ray
diffraction
analyses.
The
results
show
that
the
crystal
of
(5-ferrocenyl-2-hydroxy
-benzenecarboxylato-O,O*)titanocene(IV)
is
monoclinic
of
space
group
P2|/c,
the
cell
parameters
are
as
follows:
a
=
13.752(4)
A,
b
=
12.180(4)
A,
c
=
12.468(3)
A,
a
=
90
。,
p
=
92.42
⑵
。
,
y
=
90
。
，
V
=
2086.4(10)
A
：
D
c
=
1.586
g/cn?,
Z
=
4,
g
=
0.776
mm
\
F(OOO)
=
1024,
R|
=
0.0643,
wR?
=
0.128
&
The
crystal
of
dimethylcyclopentadienyl
5-ferrocenylsalicylatotitanium(IV)
is
monoclinic
of
space
group
P2Jc,
the
cell
parameters
are
as
follows:
a
=
14.3310(9)
A,
b=
12.5065(8)
A,
c
=
12.9406(10)
A,
a
=
90
。
，
卩
=
95.101(4)^
7
=
90
。
，
V
=
2310.2(3)
A\
Dc
=
1.513
g/cm[
Z
=
4,
g
=
0.900
mm",
F(OOO)
=
1088,
R|
=
0.0461,
wR?
=
0.104
&
Keywords:
ferrocene,
titanocene
complex,
hetero
nucleus
complex,
aromatic
acid
IV
目录
11
第一章绪论
1.1
茂钛类配合物合成方法研究进展
1
・
1
・
1
前言
1.1.2
茂钛类配合物的合成方法
1.13
茂钛杂核配合物的合成研究进展
1.2
课题的提出及意义
16
第二章二茂钛和二茂铁衍生物合成研究
・・
17
2
」
前言
17
2
・
2
实验部分
17
221
仪器及试剂
17
222
二氯二茂钛和二氯二甲基二茂钛的合成
18
2.2.2J
二氯二茂钛的合成
18
222
・
2
二氯二甲基二茂钛的合成
19
223
二茂铁芳香酸配体的合成
19
2.2.3.1
5
•二茂铁基水杨酸的合成
19
2.23.2
4
•二茂铁基苯甲酸的合成
.,19
2.233
2
•二茂铁基苯甲酸的合成
20
223.4
配合物
6
、
7
的合成
20
223
・
5
配合物
8
、
配合物
9
的合成
21
2236
乙基二茂铁和二乙基二茂铁分别和
5
•氨基水杨酸反应
22
2.23,7
结果与讨论
22
2,23,7,1
二氯二茂钛和二氯二甲基二茂钛的表征
...........................
22
2.23.7.2
二茂铁芳香酸的表征
23
2,2.3.73
烷基二茂铁水杨酸的表征
25
2.2.4
二茂铁磺酸盐的合成
29
O
2.241
合成
29
2.2A.2
单晶的培养
30
2,2.43
晶体结构的测定
30
2.24,4
讨论
35
2.3
结论
38
第三章温和条件下合成茂铁茂钛杂核配合物及其反应研究
39
3
・
1
前言
39
3,2
实验部分
40
321
仪器及试剂
40
322
溶液配制
40
323
在线监测
40
324
水杨酸二茂钛配合物的合成及表征
41
325
5
•二茂铁基水杨酸二茂钛的合成及表征,
41
3.2.5.1
配合物
13
的合成
41
3252
单晶的培养
42
3.2,53
晶体结构的测定
42
326
结果与讨论
46
327
5
•二茂铁基二甲基二茂钛的合成及表征
50
3
・
2
・
7
・
1
配合物
14
的合成
50
327.2
单晶的培养
50
•
327.3
晶体结构的测定
50
328
结果与讨论
55
329
乙基二茂铁水杨酸二茂钛的合成
58
3210
取代苯甲酸二茂钛配合物合成
59
3211
过渡性配体存在下两相合成二茂钛配合物的反应的在线监测
60
33
结论
61
