第 11 章
DESCRIPTION
第 11 章. 配位化学基础. 主要内容. 配位化合物的基本概念. 1. 配位化合物的价键理论. 2. 配位化合物的晶体场理论. 3. 配位化合物的稳定性. 4. 配位化学是在无机化学的基础上发展起来的，配位化合物（有时称络合物）是无机化学研究的主要对象之一。. 1893 年，瑞士化学家维尔纳（ A. Werner ）提出配位理论和内界、外界的概念，标志着配位化学的建立，并因此获得诺贝尔化学奖。. 11―1 配位化合物的基本概念. 11 ― 1 ― 1 配位化合物. 1 定义. - PowerPoint PPT PresentationTRANSCRIPT
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11
-
4
1
2
3
-
1893A. Werner
-
1111
1
111
-
[ Co NH3 6 ]3+[ Cu NH3 6 ]3+
[ Cr CN 6 ]3[ Co SCN 4 ]2
[ Ni CO 4 ][ Cu NH2CH2COO 2 ]
-
[ Co NH3 6 ][ Cr CN 6 ]
[ Ni CO 4 ] [ Cu NH2CH2COO 2 ]
K3[ Fe CN 6 ]
[ Co NH3 6 ]Cl3
-
2
Cl
K+
[ Co NH3 6 ]Cl3
[ Co NH3 6 ]3+
K3[ Co CN 6 ]
[ Co CN 6 ]3
[ Co NH3 6 ][ Cr CN 6 ]
[ Ni CO 4 ]
-
[ FeF6 ]3 Fe3+
[ Ni CO 4 ]
Ni
-
NH3H2OCO
N2
FIOHCN
SCN C2O42
-
3
-
N
6
6
NO
2
4
[ Co NH3 6 ]Cl3
[ Cu NH2CH2COO 2 ]
-
4
NH3H2OFCN
C2O42 en
H2NCH2 CH2 NH2
-
Cu2+
-
EDTA
2 N4 OH O
-
EDTA Ca2+
-
H2NCH2COO Cu2+
-
1112
F Cl
OH CN
O2 O22
N3 N3
S2 H
-
SCN
NCS
C6H5
NO2
ONO
SO42
py
-
NO
CO
H2O
NH3
O2
en
Ph3P
-
1
III
[ Co NH3 6 ]Cl3
-
Cu2 [ SiF6 ]
IV
[ Cu NH3 4 ] SO4
II
-
2
-
3
1
II
[ PtCl2 Ph3P 2 ]
-
2
II
K[ PtCl3 NH3 ]
-
3
III
[ Co NH3 5 H2O ]Cl3
-
4
(II)
[ Pt py NH3 NH2OH NO2 ]Cl
-
5
NH2 NO2 NH2
II
[ Pt NH3 2 NO2 NH2 ]
-
-
-
- [ ]
[ NH3 5Cr-OH-Cr NH3 5 ]Cl5
- [ ]
[ CO 3 Fe- CO 3-Fe CO 3 ]
-
-
-
-
PtCl2 NH3 C2H4
K[ PtCl3 C2H4 ]
-
1113
-
1
1
-
SO42 Ba2+ ;
Br Ag+
[ CoBr NH3 5 ]SO4
[ CoSO4 NH3 5 ]Br
-
H2O
[ CrCl H2O 5 ]Cl2H2O
[ Cr H2O 6 ]Cl3
-
2
[ Co NH3 6 ][ Cr CN 6 ]
Co3+ Cr3+
[ Cr NH3 6 ][ Co CN 6 ]
-
3
NO2
N NO2
O ONO
-
[ Co NO2 NH3 5 ]Cl2
[ Co ONO NH3 5 ]Cl2
-
2
1
4 [ PtCl2 NH3 2 ]
-
[ PtCl2 NH3 2 ]
-
-
-
trans -
cis -
-
M abcd 4
Mab30Ma2b22Mabc22Mabcd3 -
M abc 6
Ma2b4 2b
a
b
b
b
a
b
b
b
b
a
a
- Ma3b32
b
b
a
b
a
a
b
a
b
a
a
b
- Mab2c33
b
c
b
c
c
a
b
a
b
c
c
c
b
a
b
c
c
c
-
3
Ma2b2c25a
c
a
c
b
b
b
c
b
c
a
a
b
a
b
a
c
c
b
c
c
b
a
a
a
b
c
c
b
a
-
2
-
Ma2b2c2
a
b
c
a
b
c
a
b
c
a
b
c
-
cis - [ Cr en 2Cl2 ]+
Cl
N
Cl
N
N
N
Cl
N
Cl
N
N
N
-
[ Co en 3 ]3+
N
N
N
N
N
N
N
N
N
N
N
N
-
Mabcd
A
B
C
D
A
B
C
D
-
112
-
1121
-
[ Ag NH3 2 ]+
2 sp
[ Fe CO 5 ]
5 dsp3
[ Ni CN 4 ]2
4 dsp2
[ Zn NH3 4 ]2+
4 sp3
[ Cu CN 3 ]2
3 sp2
[ Fe SCN 5 ]2
5 sp3d
[ Co NH3 6 ]2+
6 sp3d2
[ Co CN 6 ]3
6 d2sp3
-
1122
ns np nd
n1 d ns np
-
1 ns np nd
111
Fe 3d64s2
Fe3+ 3d5
[ Fe H2O 6 ]3+
[ Fe H2O 6 ]3+
-
Fe3+ 3d5
3 d
4 d
4 s
4 p
3 d
sp3 d2
-
[ Fe H2O 6 ]3+
ns np nd
[ Fe H2O 6 ]3+
sp3d2
-
Ni 3d8 4s2
CO Ni 3d10 4s0 4s 4p sp3
[ Ni CO 4 ]
112
-
3 d
4 s
4 p
3 d
4 s
4 p
3 d
sp3
-
[ Ni CO 4 ]
ns np nd
[ Ni CO 4 ]
sp3
-
111112 ns np nd
CO
COCN NO2
-
H2O
FClH2O
NH3 en
-
Co 3d74s2
Co3+ 3d6
CN Co3+ 6 d 2 3d d2sp3
[ Co CN 6 ]3
113
2 n1 d ns np
-
3d
4s
4p
3 d
3 d
4 s
4 p
d2sp3
-
[ Co CN 6 ]3
n1 d
-
Pt 5d9 6s1
Pt2+ 5d8
CN Pt2+ 8 d 1 5d dsp2
[ Pt CN 4 ]2
114
-
5 d
6 s
6 p
5 d
dsp2
5 d
6 s
6 p
-
113 114n1d
[ Pt CN 4 ]2
dsp2
-
1123
B
n n + 2
B
n
-
n
n n + 2
B
-
NH3
n = 0
Co3+ 3d6
[ Co NH3 6 ]3+
Co d
[ Co NH3 6 ]3+
= 0 B
-
Co3+ 4
NH3
n = 0
-
1124
E E
-
d P
[ Fe CN 6 ]3
d 2 2P
-
2P ,
-
P + E > E
P + E < E
P
0
E
E
P
0
E
E
-
1125
-
1
CO C sp3
[ Ni CO 4 ]
Ni 3d84s24p0 3d104s04p0 sp3
-
[ Ni CO 4 ]
-
Ni d
CO *
dxy
+
+
*
px
-
Ni d
CO *
dp
Ni CO
+
-
2
CN CO
d
* d
CN
C
d CN
*
-
3
Zeise K[ PtCl3 C2H4 ]H2O
-
d *
+
-
113
1131 d
5 3d
-
d
x2y2
+
+
y
x
+
+
z
y
d
yz
d
xz
+
+
z
x
d
xy
+
+
y
x
-
3d
-
1 d
6 4
d
-
1
xyz 6
-
d d
5 d
d
-
d d eg
d
x 2 y 2
d
z 2
d
x 2 y 2
d
z 2
-
d
x2y2
+
+
y
x
-
d d t2g
d
xy
d
xz
d
yz
d
xy
d
xz
d
yz
-
+
+
z
y
d
yz
d
xz
+
+
z
x
d
xy
+
+
y
x
-
d d
d
d
x 2 y 2
d
z 2
d
xy
d
xz
d
yz
d
-
o
o
d
d
o
d
x 2 y 2
d
z 2
d
xy
d
xz
d
yz
-
2
4
-
dxzdyzdxy
-
d d t2
d
xy
+
+
y
x
-
d
x 2 y 2
d
z 2
-
d e
d
x2y2
+
+
y
x
-
t
t o
d
d
t
d
x 2 y 2
d
z 2
d
xy
d
xz
d
yz
-
3
4
x
y
-
d
x 2 y 2
d
z 2
xOy
d
xy
xOy
d
xz
d
yz
-
p > o > t
p
d
xy
d
xz
d
yz
d
z2
p
d
x 2 y 2
-
2
1
p > o > t
-
2
[ Fe CN 6 ]3
[ Fe CN 6 ]4
>
-
3
d
[ Hg CN 4 ]2
[ Zn CN 4 ]2
>
-
4
I < Br< SCN < Cl < F< OH
-
< < <
I < Br< SCN < Cl < F< OH
-
3 d
d
-
115 d4
d4
P
-
d
P
> P
d
d
-
dr
< P
d
d
-
P
1 cm
E = h
-
d
[ Fe CN 6 ]4
= 33000 cm1 P = 15000 cm1
[ Fe H2O 6 ]2+
116
= 10400 cm1 P = 15000 cm1
-
Fe2+ d6
H2O < P
FClH2O
[ Fe H2O 6 ]2+
< Pd
d d 4 d 2
d
d
-
CN > P
COCNNO2
d
d
[ Fe CN 6 ]4
> Pd
d d 6 d 0
-
1132
1 d
5 d d
d d 5 d
-
1
o
d
d
d
d
3 E + 2 E 0
d
d
E E o
-
o 10 Dq
d
5
3
E o
d
5
2
E o
d
d
E 6 Dq
E 4 Dq
-
2
t
d
d
E E t
d
d
d
d
3 E + 2 E 0
-
t 10 Dq
9
4
t o
d
E 4 Dq
d
E 6 Dq
d
5
3
E o
d
5
2
E o
-
2
d d E E E 0
crystal field stabilization energy CFSE
CFSE E E 0 E
-
117 d5 CFSE
d5
d
d
-
E 4 Dq 5 + 2P
20 Dq + 2P
CFSE E E
0 20 Dq + 2P
20 Dq 2P
2 2P
-
118 d6 CFSE
d6
d
d
-
E 6 Dq 3 + 4 Dq 3
6 Dq
CFSE E E
6 Dq
0 6 Dq
-
Fe2+ d6
> Pd
d
d
[ Fe CN 6 ]4
119 33000 cm1
P 15000 cm1 CFSE
-
49200 cm1
5
2
CFSE 0 [ 6 + 2P ]
5
12
2P
5
12
33000 cm1 2 15000 cm1
-
M2+
| H | M2+ d
d
| H |
0 1 2 3 4 5 6 7 8 9
-
H2O
d
| H |
M2+g+ 6 H2Ol [ M H2O 6 ]2+aq
-
d
| H |
0 1 2 3 4 5 6 7 8 9
-
M2+ d0 d10
CFSE Dq
d
-
| H | CFSE
d0d5d10
d3d8
d 0 1 2 3 4 5 6 7 8 9 10
CFSE / Dq 0 4 8 12 6 0 4 8 12 6 0
d 0 1 2 3 4 5 6 7 8 9 10
CFSE / Dq 0 4 8 12 6 0 4 8 12 6 0
d 0 1 2 3 4 5 6 7 8 9 10
CFSE / Dq 0 4 8 12 6 0 4 8 12 6 0
-
d
| H |
0 1 2 3 4 5 6 7 8 9
-
1133
1
-
/nm
400435
435480
480490
490500
500560
560580
580595
595605
605750
-
2 d d
d d d d d
d d
d d
-
Ti3+ 3d1
d
d
[ Ti H2O 6 ]3+
1110
d 0
d 1
Ti3+ 3 d d
-
Ti3+
o d
d
d 0
d 1
[ Ti H2O 6 ]3+
d
d
-
d
d
[ Mn H2O 6 ]2+
1111
d 2
d 3
Mn2+ 3d 5 H2O
Mn2+ 5 d
-
d
d
[ Mn H2O 6 ]2+
Mn2+ d
d 3
d 2
dd
-
3
CuI3d10CdII4d10
LaIII5d0 TiIV3d0
d0 d10
dd
dd
ZnI23d10
-
d10 CdI2
HgI2
MI2 M2+
I
-
ZnI2 Zn2+ I
CdI2 HgI2 ZnI2
-
CdI2
HgI2
-
VO3 CrO42
MnO4
-
AgI
AgI
AgI
-
1134
Cu2+ d9
NH3 4p
dsp2
[ Cu NH3 4 ]2+
-
3 d
4 s
4 p
3 d
4 s
4 p
3 d
4 p
dsp2
-
dsp2
d
[ Cu NH3 4 ]2+
[ Cu NH3 4 ]2+
CuII
-
d
[ Cu NH3 4 ]2+
[ Cu NH3 4 ]2+
-
d
d
d
x 2 y 2
d
x 2 y 2
-
z xOy
-
d
z 2
d
d
d
z 2
-
z z
-
z
[ Cu NH3 4 ]2+
-
d
Cu2+ d 9
d
x 2 y 2
d
z2
d
xy
d
xz
d
yz
d
x 2 y 2
d
z 2
-
[ Pt Cl4 ]2
d 2
d 6
Pt2+ d8
d
x 2 y 2
d
z 2
Pt
-
d
x 2 y 2
d
z2
d
xy
d
xz
d
yz
d
x 2 y 2
d
z 2
d
x 2 y 2
-
114
-
1141
1
K
[ Ag NH3 2 ]+
Ag+ + 2 NH3
[ Ag NH3 2+ ]
K
[ Ag+ ] [ NH3 ]2
-
K
K
[ Ag NH3 2+ ]
K
[ Ag+ ] [ NH3 ]2
-
K
K
1
K
K
[ Ag+ ] [ NH3 ]2
[ Ag NH3 2+ ]
[ Ag NH3 2 ]+
Ag+ + 2 NH3
-
NH3H2O AgNO3
1.0 moldm3
0.10 moldm3
[ Ag NH3 2 ]+
[ Ag NH3 2 ]+
1112 0.20 moldm3 AgNO3
2.0 moldm3 NH3H2O
Ag+NH3
K 1.1 107
-
[ NH3 ] 1.0 0.20moldm3
0.80 moldm3
[ Ag NH3 2 ]+
0.10 moldm3
[ Ag NH3 2 ]+
[ Ag NH3 2 ]+
Ag+
-
c0 / moldm3 0.10 1.0
c / moldm3 x 0.80 0.10
1.1 107
x 1.4 10 8
[ Ag+ ] 1.4 108 moldm3
[ Ag NH3 2 ]+
Ag+ + 2 NH3
x 0.80 2
0.10
[ Ag NH3 2+ ]
K
[ Ag+ ] [ NH3 ]2
-
2
1
K3[ Fe C2O4 3 ]
FeCl3 K2C2O4
K3[ Fe C2O4 3 ]
FeCl3 + 3 K2C2O4
+ 3 KCl
K3[ Fe C2O4 3 ]
[ FeCl4 ]
-
K3[ Fe C2O4 3 ]
H2C2O4 C2O42
H+
K3[ Fe C2O4 3 ]
+ 4 HCl
K[ FeCl4 ] + 2 KHC2O4 + H2C2O4
-
pH
+ NH3H2O
Cu NH3 4 SO4
2 CuSO4 + 2 NH3H2O
Cu OH 2CuSO4 + NH4 2SO4
Cu OH 2CuSO4
+ H2SO4
+ H2SO4
CuSO4
-
2
Mn+
KspK
Mn+
-
1113 CuI 1.0 moldm3 NH3H2O
K KKsp
1.27 1012 7.25 1010
9.21 10 2
CuI Cu+ + I Ksp
[ Cu NH3 2 ]+
CuI + 2 NH3H2O + I
[ Cu NH3 2 ]+
Cu+ + 2 NH3 K
-
[ NH3 ] 1.0 2x
9.21 102
x 0.19
CuI 1.0 moldm3 NH3H2O
0.19 moldm3
1.0 2x 2
x2
[ Cu NH3 2 ]+
[ I ] x
[ Cu NH3 2+ ]
K
[ NH3 ]2
[ I ]
-
3
+ z e
E
E E +
0.059 V
z
[ ]
[ ]
lg
-
E
E
-
[ HgI4 ]2/ Hg
[ HgI4 ]2 + 2 e Hg + 4 I
[ HgI42] [ I] 1 moldm-3
1114
Hg2+ + 2 e Hg E 0.85 V
[ HgI4 ]2 K 6.76 1029
Hg2+ + 2e Hg
[ HgI4 ]2/ Hg E
-
Hg2+ + 4 I [ HgI4 ]2
[ I ] [ HgI42 ] 1 moldm-3
[ HgI4 ]
[ Hg2+ ] [ I ]4
K
K
1
[ Hg2+ ]
1
6.76 10 29
-
Hg2+ + 2 e Hg
0.30 V
E E +
0.059 V
z
lg [ Hg2+ ]
1
6.76 1029
E 0.85 V +
0.059 V
2
lg
[ HgI4 ]2/ Hg E 0.30 V
-
Co3+ + e Co2+ E 1.83 V
[ Co NH3 6 ]3+
1115
Co3+ + 6 NH3
K1 1.58 1035
[ Co NH3 6 ]2+
Co2+ + 6 NH3
K2 1.29 105
[ Co NH3 6 ]3+
[ Co NH3 6 ]2+
+ e
E
-
1
K
1.58 1035
[ Co3+ ]
1
[ Co NH3 6 ]3+
Co3+ + 6 NH3
K1 1.58 1035
[ Co NH3 6 ]2+
Co2+ + 6 NH3
K2 1.29 105
1
K
1.29 105
[ Co2+ ]
1
-
Co3+ + e Co2+
0.054 V
[ Co3+ ]
[ Co2+ ]
lg
0.059 V
z
E E +
1.58 1035
1
1
1.29 105
E +
0.059 V
1
lg
[ Co NH3 6 ]3+
[ Co NH3 6 ]2+
+ e
E 0.054 V
-
4
Fe3+
F
Fe3+ SCN
[ Fe SCN n ] 3n
+ m F [ FeFm ] 3m + n SCN
[ FeFm ] 3mm = 1 ~ 6
[ Fe SCN n ] 3n
n = 1 ~ 6
-
Fe3+
SCN
Co2+ SCN
[ Fe SCN 4 ]
[ Co SCN 4 ]2
+ Fe3+ + Co2+
-
1142
1
1
[ Fe CN 6 ]3
[ Fe CN 6 ]4
>
[ Co NH3 6 ]3+
[ Co NH3 6 ]2+
>
-
d
2
[ Pt NH3 6 ]2+
[ Ni NH3 6 ]2+
>
[ Zn NH3 4 ]2+
[ Hg NH3 4 ]2+
>
-
2
[ Co CN 6 ]3
[ Co NH3 6 ]3+
>
[ Cu NH3 4 ]+
[ Cu CN 4 ]3
>
-
3
5 6
Ca2+
EDTA
-
EDTA 6 Ca2+
5 5
2 N4 O
-
Al3+
8
8 Al3+
-
4
-
H2ONH3 < ClBr < SCNNO2
-
NH3
[ Pt Cl4 ]2
[ Pt NH3 Cl3 ]
NH3
NH3
-
NH3 NH3
Cl Cl
Cl
Cl NH3
NH3
-
5 18
18
18
EAN
9
5 d 1 s 3 p
-
[ Ni CO 4 ]
Ni 3d84s
10 4 CO
8 18
[ Fe CO 5 ]
Fe 3d64s2
8 5 CO
10 18
[ Ni CO 4 ]
[ Fe CO 5 ]
-
1143
1
-
La3+ Ce4+ Ti4+
917e
Cr3+Mn2+Fe3+
IAIIA
Na+Mg2+
IIIAIVA
B3+Al3+Si4+
-
Cu+Ag+Cd2+Hg2+
Hg22+Tl+Pt2+
-
Cr2+Fe2+Co2+Ni2+Cu2+
Zn2+Sn2+Pb2+Sb3+Bi3+
-
FClH2OOHO2SO42NO2ClO4NH3
-
IS2CNSCNCO
S2O32C6H6
-
BrSO32N2NO2
-
2
1116
HgI42 > HgBr42 > HgCl42 > HgF42
AlF63 > AlCl63 > AlBr63 > AlI63
-
Hg2+ I F Hg2+
Al3+ F I Al3+
-
1117 AgF
AgBr
AgF
Cl
AgCl
Br
I
AgI
S2
Ag2S
[ Ag NH3 2 ]+
NH3
[ Ag CN 2 ]
CN
[ Ag S2O3 2 ]3
S2O32
-
Ag+
[ Ag NH3 2 ]+
[ Ag CN 2 ]
[ Ag S2O3 2 ]3
<
-
IA IIA
H2O
-
[ Pt Cl4 ]2
[ Ag NH3 2 ]+
[ Zn NH3 4 ]2+
[ Ni CN 4 ]2
[ Cu CN 3 ]2
[ Fe H2O 6 ]3+
[ Co CN 6 ]3
[ Cu NH2CH2COO 2 ]
[ Pt py NH3 NH2OH NO2 ]Cl
[ Pt NH3 2 NO2 NH2 ]
[ NH3 5Cr-OH-Cr NH3 5 ]Cl5
[ CO 3 Fe- CO 3-Fe CO 3 ]
[ Fe CN 6 ]3
[ Fe CN 6 ]4
[ Ti H2O 6 ]3+
[ Mn H2O 6 ]2+
[ Cu NH3 4 ]2+
[ Ag NH3 2+ ]
K
[ Ag+ ] [ NH3 ]2
[ Fe SCN 6 ]3
[ Fe SCN n ] 3n
-
Cu2 [ SiF6 ]
d
d
[ FeFm ] 3mm = 1 ~ 6
[ Co NH3 6 ]Cl3
K3[ Fe CN 6 ]
[ Co NH3 6 ][ Cr CN 6 ]
[ Ni CO 4 ]
K3[ Co CN 6 ]
[ Co CN 6 ]3
[ Co NH3 6 ]3+
[ Cu NH3 4 ] SO4
[ PtCl2 Ph3P 2 ]
K[ PtCl3 NH3 ]
[ Co NH3 5 H2O ]Cl3
[ Cr NH3 6 ][ Co CN 6 ]
d
x 2 y 2
d
z 2
d
xy
d
xz
d
yz
d
d
5
3
5
2
d 0
d 1
[ Cu CN 4 ]3
[ Fe CO 5 ]
K3[ Fe C2O4 3 ]
[ Cu NH3 2 ]+
NH
3
Cl
Cl
Cl
Pt
NH
3
Cl
Cl
Cl
Pt