2 2 4

3 3 6
4 2 6
( ) 2 [ ( ) ]
3 [ ]
2
Be OH NaOH Na Be OH
AlF NaF Na AlF
SiF HF H SiF
+
+
+
2 3
3 3
3 3 2
. ( ) . ( )
.5
.5 .
KCN Fe CN Fe CN XanhBeclin Diesbach XVIII
CoCl NH amoniacat puapureo RED XIX
CoCl NH H O amoniacat rozeo PINK XIX



Cr(OH)
3
lng tnh
In acid In base
Chromate and Dichromate Ions
+5
+4
+3
+2
THUYT MCH
W. Blomstrand & Jorgensen
1884
3
NH Cl
Co
3 3
NH NH
3 3
3
NH NH Cl
NH Cl

3 3
.6 CoCl NH
3 3
.5 CoCl NH
3 3
.4 CoCl NH
Cl
Co
3
NH
3 3 3
3
NH NH NH Cl
NH Cl

Cl
Co
3
NH
3 3 3
NH NH NH Cl
Cl

THUYT PHI TR-1892
A. Werner, 1866-1919
Noben ha hc nm 1913
1. C th c Ha tr chnh v Ha tr ph trong nguyn t.
Ha tr chnh tng ng vi khi nim s oxi ha.
Ha tr ph tng ng khi nim s phi tr.
2. Nguyn t to phc c xu hng bo ha cc ha tr
chnh v ha tr ph. Ha tr chnh ch c bo ha
bng anion, cn ha tr ph c bo ha bng anion v
phn t trung ha.
3. Ha tr ph c phng xc nh trong khng gian.
3 3
.6 CoCl NH
3 3
.5 CoCl NH
3 3
.4 CoCl NH
3
3
Cl NH
NH
3
NH
Co
3
Cl
NH
3
3
NH
Cl NH
3 3
Cl
NH NH
Cl Co
3 3
3
Cl
NH NH
NH
3 3
Cl
NH NH
Co
3 3
Cl
NH NH
Cl
CHNG 10. PHC CHT
Mt s nh ngha
1. Phc cht
2. S phi tr ca nhn trung tm
3. Dung lng phi tr ca phi t
4. ng phn phc cht: cis-trans, quang hc, phi tr, ion ha, lin kt
Hng s in ly v hng s bn ca ion phc
Thuyt lin kt ha tr - The Localized Electron Model
Thuyt trng tinh th - The Crystal Field Model
1. S tch cc orbital ha tr d ca nhn trung tm bi trng cc phi t trong
ion phc 8 mt u AL
6
x+
2. S phn phi cc e ha tr d trong ion phc 8 mt u
3. Nng lng lm bn bi trng tinh th Ws
4. Thuyt trng tinh th p dng cho ion phc bn mt u AL
4
x+
5. Cc yu t nh hng n thng s tch
6. S to thnh cc ion phc c cu trc khc
7. u nhc im ca thuyt trng tinh th
Thuyt orbital phn t - The Molecular Orbital Model
KHI NIM
Coordination Chemistry
Hp cht phi
tr (phc cht)
l hp cht ha
hc m phn t
ca n cha ion
phc
Ion phc
L tp hp cc cation v anion
C ion trung tm l kim loi
C cc phi t
Trong ion phc-complex tn ti nguyn t
trung tm (nhn trung tm), thng l cc ion
kim loi chuyn tip v bao quanh n l cc
nguyn t, phn t hay ion lin kt gi l phi
t-ligands
Ion phc c gi l cu ni-coordination
sphere, l vng cha nguyn t hoc ion
trung tm v cc phi t.
S phi tr-coordination number l s lin
kt ca nhn trung tm vi cc phi t
Phc mang in tch c gi l ion phc-
complex ion.
Cht m c cha mt hoc nhiu ion phc
c gi l hp cht phi tr-coordination
compound.
[CoCl(NO
2
)(NH
3
)
4
]
+

What are the coordination number and the
oxidation number of the central atom in
[CoCl
4
(NH
3
)
2
]

[Cr(OH)
4
(H
2
O)
2
]
-
S phi tr bin
i ph thuc
vo bn cht
ca phi t,
nng , nhit
, cu ngoi.
Cu
2+
, Ni
2+
, Zn
2+

c s phi tr
bin i. Co
3+
,
Cr
3+
, Rh
3+
, Ir
3+
,
Pt
4+
, Ir
4+
c s
phi tr 6 khng
i
Nhiu nguyn t v ion, nht l cc kim loi chuyn
tip, c nhiu orbital trng do c th nhn cc cp
in t.
Dung lng phi tr ca phi t l s lin kt ca 1
phi t lin kt vi nhn trung tm.
Phi t c dung lng phi tr bng 1 gi l phi t
n cng-monodentate ligands, nh NH
3
, OH
-
, Cl
-
,
NO
2
-
, CN
-
Phi t c dung lng phi tr ln hn 1 gi l phi
t a cng-polydentate ligand, nh H
2
N-CH
2
-CH
2
-
NH
2
, C
2
O
4
2-
.
Phi t a cng lin kt vi nhn trung tm to
thnh vng 5 hoc vng 6 gi l phc cht vng
cng-chelate.
Dung lng phi tr ca phi t
Chelates
Metals and Chelates in Living Systems
1. Trong tn phc cht, u tin l phi t, ri n nguyn
t/ion trung tm, tt c chng c vit lin nhau.
2. Khi vit tn phc cht t cng thc, tn cc phi t sp xp
theo th t bng ch ci m khng tnh n cc s u ng.
Khi vit cng thc t tn, cc phi t anion t trc phi t
trung ha v tun theo trt t bng ch ci.
3. S phi tr ca phi t t trc phi t. Nu tn ca phi t
bn thn n c ch s, th t du ngoc n cho tn phi
t v ch s phi tr ca phi t.
4. Tn ca cation phc l tn ca nguyn t trung tm. Tn ca
anion phc thng thm ui ate vo cui nguyn t trung
tm. Trong mt s trng hp, s oxi ha ca nguyn t
trung tm c vit bng ch s Lam trong ngoc n.
5. Khi vit cng thc hay tn ca phc cht, phi t cc ion
theo th t cation ri n anion.

Cch gi tn phc cht
Vit tn ca:
[CrCl
2
(NH
3
)
4
]
+

Tetraamminedichloro-crom(III) ion
K[PtBrCl
2
NH
3
].
Kalium Amminebromodichloro-platinum(II)
Vit cng thc ca:
triamminechlorodinitrito-O-platinum(IV) ion
[PtCl(ONO)
2
(NH
3
)
3
]
+
sodium hexanitrito-N-cobaltate(III).
Na
3
[Co(NO
2
)
6
]
HNG S IN LI V HNG
S BN CA ION PHC
1. Trong nc, phn t phc cht phn li
thnh ion cu ngoi v ion cu ni.
2. Sau ion phc in li yu tng nc
ra cc phi t.
3. i lng c trng cho s in li ca
ion phc gi l:
hng s bn tng cng-
nb
v
hng s bn tng nc-K
nb
.
| |
3 3 2
( ) 2 ( ) ( ) ( ) ( ) AgCl s NH aq Ag NH aq Cl aq
+

+ +
| |
3 3 2
( ) 2 ( ) ( ) ( ) ( ) AgCl s NH aq Ag NH aq Cl aq
+

+ +
11
1.810
( ) ( ) ( )
T
AgCl s Ag aq Cl aq

=
+
+
| |
7
2
1.610
3 3 2
( ) 2 ( ) ( ) ( )
b
Ag aq NH aq Ag NH aq
| + =
+
+
| |
| |
3 2
2 1 2
2
3
( )
( )
b b
Ag NH
K K
Ag NH
|
+
+
= =
(

| |
| |
3
1
3
( )
b
Ag NH
K
Ag NH
+
+
=
(

| |
| | | |
3 2
2
3 3
( )
( )
b
Ag NH
K
Ag NH NH
+
+
=
1 2
( ... )
nb n b
K K K | =
ln
o o o
n
G RT H T S | A = = A A
Phc bn khi
n
cng ln, G
o
cng nh
H
o
cng b v S
o
cng ln


| |
| |
. . .
( ) ( ) ( )
x
x
n
x
x
n
A aq nL aq AL aq
A k nL k aq AL k aq
+
+
+
+
+
+ + |
+ + +
o
E
x
A L
n H
+

A ,
x
n
o
h AL
H
+
A
,
x
o
h A
H
+
A
,
o
h L
H A
o
H A
,
, ,
x x
x
n
A L
o o o o o
E h L
h AL h A
H H n H H H
+ +
+

A = A A A A
2 1
o o o
S S S A = A A

| | | |
2 2
0
2 6 4 2
( ) . 4 . ( ) . 6
o
S
Ni H O aq CN aq Ni CN aq H O
+
A >
+ +
| | | |
2 2
0
3 6 3 3
( ) 3 6
o
S
Ni NH En NiEn NH
+ +
A >
+ +
Phn ng lm gim in tch ca ion phc l tng S ca h
Phn ng to vng phc t phi t n cng l tng S ca h
? C kt ta khng trong dung dch cha cc cht sau:
0.1 mol AgNO
3
ha tan trong 1 lt nc cha NH
3
1M.
Nu 0.01 mol NaCl c thm vo dung dch th c kt
ta AgCl khng ?
Gi s
2b
rt ln:
Initial conc. 0.10 M 1.00 M 0 M
Change -0.10 M -0.20 M +0.10 M
Eqlbrm conc. (~0) M 0.80 M 0.10 M
| |
3 3 2
( ) 2 ( ) ( ) ( ) Ag aq NH aq Ag NH aq
+
+
+
[Ag
+
] tuy rt nh nhng khng th bng 0, s
dng hng s bn tng cng -
2b
ca phc
tnh [Ag
+
]:
0.10

(1.6
.
10
7
)(0.80)
2
x = [Ag
+
] = = 9.8
.
10
-9
M

= 1.6
.
10
7
[Ag(NH
3
)
2
]
+
[Ag
+
] [NH
3
]
2
0.10-x

x(0.80 + 2x)
2
0.10

x(0.80)
2
= ~
2b
=
Initial concs. 0 M 0.80 M 0.10 M
Changes +x M +2x M -x M
Eqlbrm conc. x M 0.80 + 2x M 0.10 - x M
| |
3 3 2
( ) 2 ( ) ( ) ( ) Ag aq NH aq Ag NH aq
+
+
+
So snh tch nng ion vi tch s tan T
xem c kt ta hay khng:
= (9.8
.
10
-9
)(1.0
.
10
-2
) = 9.8
.
10
-11
[Ag
+
] [Cl
-
]

T
TG
=
T = 1.8
.
10
-10

T
TG
< T
AgCl khng to kt ta trong iu kin ny.
THUYT LIN KT HA TR
Valence Bond Theory
THUYT LIN KT HA TR
The Localized Electron Model
- Lin kt ca ion trung tm vi
cc phi t l lin kt cho nhn
- Ion trung tm c s lai ha
- Cc AO trng ca ion trung tm
nhn cc cp e cha phn chia
ca cc phi t
- Phi t l cht cho (donor), nhn
trung tm l cht nhn
(acceptor)
- 1927 thuyt axit-bazo ca Liuyt
- N. Sidgwick, 1873-1952, UK, vn dng cho phc cht


3 3 3 3
( ) : ( ) BF k NH F B NH r + =
3 3 3
3 3
3
3 3 3
6:
NH NH NH
Co NH Co
NH NH NH
+ +
+
+ =
|
3 3 2
2 [ ( ) ] Cu NH Cu NH
+ +
+ =
10
3
(3 )
d
Cu d
+
|+ |+ |+ |+ |+
3
4s
NH
--
|+
l
3
4p
NH
--
|+
l
sp
2 2
4
4 [ ] Co Cl CoCl
+
+ =
2 7
3
(3 )
d
Co d
+
|+ |+ | | |
4s
Cl
--

|+
l
4p
Cl Cl Cl
-- -- --

|+ |+ |+
l l l
sp
3
2 2
4
4 [ ] Pt Cl PtCl
+
+ =
2 8
5
(5 )
d
Pt d
+
|+ |+ |+ |+
6s
Cl
--

|+
l
6p
Cl Cl
-- --

|+ |+
l l
dsp
2
Cl
--

|+
l
3 3
3 3 6
6 [ ( ) ] Co NH Co NH
+ +
+ =
3 6
3
(3 )
d
Co d
+
|+ |+ |+ |+ |+
3
4s
NH
--
|+
l
3 3 3
4p
NH NH NH
-- -- --
|+ |+ |+
l l l
d
2
sp
3
s lai ha trong

3 3
NH NH
-- --
l l
3 3
6
6 [ ] Co F CoF
+
+ =
3 6
3
(3 )
d
Co d
+
|+ | | | |
4s
F
--

|+
l
4p
F F F
-- -- --

|+ |+ |+
l l l
sp
3
d
2
s lai ha ngoi

4d
F F
-- --

|+ |+
l l
3
2 6
3
6
2
3 6
[ ( ) ]
[ ]
[ ( ) ]
Fe H O
FeF
Ni NH
+

+
U IM V HN CH
THUYT LIN KT HA TR
u im:
- M t n gin v c th cc lin kt
trong phc cht
- Gii thch c t tnh ca phc cht
Hn ch:
- Khng gii thch c mu sc ca
phc cht
THUYT TRNG TINH TH
Crystal Field Theory
THUYT TRNG TINH TH
Crystal Field Theory
1. Phc cht tn ti v bn do tng tc tnh
in gia nhn trung tm v cc phi t
2. Phi t l in tch im khng c cu trc
3. Nhn trung tm c cc AO-d ha tr ng
nng lng s b phn tch thnh cc mc
khc nhau do tc dng ca trng to bi cc
phi t
4. Phc cht c i xng xc nh v c m
t bng cc nh lut ca c hc lng t
Xt trng phi t trong
phc bt din AL
6
x+
A
S tch cc orbital ha tr d ca nhn
trung tm bi trng cc phi t
Cc orbital
mu vng
c nng
lng cao
hn cc
orbital mu
do tc
dng ca
trng phi
t
-thng s tch
e
g
- E
2
t
2g
E
1

o
[cm
-1
]; 1 cm
-1
= 11,9 J/mol
=E
2
E
1

3E
1
+ 2E
2
= 0
E
2
= 0.6
E
1
= - 0.4

d

d
c
Fig. 22.17

o
| | |+
P
P l nng lng cp i ca electron
L nng lng cn thit chuyn 2 e c thn
vi spin cng du t 2 orbital cng nng lng
vo 1 orbital m chng c spin ngc du
nhau
>
<
< P: HS
> P: LS
Nng lng bn ha bi trng tinh th
(LB) s gim nng lng ca cc e in vo
orbital d c nng lng thp so vi nng lng
trung bnh ca orbital trong trng tinh th
s cng ln th phc cht cng bn.
s ch ng gp vo nng lng lin kt ch
khng phi l nng lng lin kt trong ion
phc.
Ligand-filed stabilization
energies (LFSE)
1 2
(0.4 0.6 )
s O
n n o = A

s
- nng lng bn ha bi trng tinh th
n
1
- s e trn cc orbital t
2g (E1 bn di)
n
2
- s e trn cc orbital e
g

HiU NG JAHN-TELLER
1937
Trng thi e suy bin ca
1 phn t khng thng
hng l khng bn,
phn t s bin dng
hnh hc gim tnh
i xng v suy bin


High-
spin:
electrons
can occupy
both low-
and high-
energy
orbitals.
2 1
2 0
[ ( )] 11000 Cr H O cm
+
A =
2 1
2 6 0
[ ( ) ] 25000 Mo H O cm
+
A =
2 1
2 6 0
[ ( ) ] 30000 W H O cm
+
A =
3 1
2 0
[ ( )] 20500 Cr H O cm
+
A =
A for Tetrahedral Complexes vs Square Planar
A
Tetrahedral
= 4/9 A
Octahedral
so
Tetrahedral Complexes are Usually High Spin
Square Planar Complexes are Always Low Spin
Fig. 22.23

t
1 2
(0.6 0.4 )
s t
n n o = A
Square Planar Crystal Field
Fig. 22.24
Orbitals split differently,
depending on the geometry
of the ligand field.
TNH CHT T CA PHC
Phc cht c e c thn l thun
t.
Phc cht khng c e c thn
l nghch t.
Moment t spin:

( 2)
S B
n n = +
n s e c thn
24
9.274 10 /
2
B
e
e
J T
m

= =
Cc ion c cu hnh e sau s khng chuyn e trogn vng VIS:
A noble-gas electron configuration.
An outer shell with 18 electrons.
An 18 + 2 configuration (for example, Sn
2+
).
Mu ca ion phc v hp
cht phi tr
[ ]
A A
hC
h N N J v

A = =
34 8
23
7
(6.61 10 ) (3 10 / )
/ (6.023 10 / ) 239 /
5 10
Js m s
J ion ion mol kJ mol
m

| |
A = =
|

\ .
S hp th nh sng v
nguyn nhn to mu sc
nh sng
vng b hp
th
cn li nh
sng xanh i
qua lm dung
dch c nhn
thy mu xanh
nh sng xanh
b hp th
cn li nh sng
vng i qua lm
dugn dch c mu
vng
blue: 400-490 nm

yellow-green: 490-580 nm

red: 580-700 nm
Quan
h
gia
cht
hp
th
v
mu
quan
st
nh hng ca phi t ln
mu ca hp cht phi tr
U IM V HN CH
THUYT TRNG TINH TH
u im:
- L m hnh n gin v d hiu
- Gii thch c nhiu tnh cht ph hp vi thc
nghim: tnh c mu, t tnh
Hn ch:
- Coi phi t l in tch im khng c cu trc: phn
t trung ha H
2
O, NH
3
to trng mnh hn anion
OH
-
, Cl
-
, F
-
; H
2
O c cc mnh hn NH
3
nhng to
trng yu hn; CN
-
bn knh nh hn F
-
nhng to
trng mnh hn nhiu
- Khng gii thch c ph chuyn dch in tch,
khng cp n lin kt Pi trong phc vi CO,
anken, ankin, xiclopentadien
THUYT ORBITAL PHN T
The Molecular Orbital Model
- Phn t phc cht l 1 ht thng nht gm nguyn
t trung tm v cc phi t
- Chuyn ng ca e trong phn t m t bng hm
sng MO
- MO l t hp tuyn tnh cc AO ca nguyn t
trung tm v phi t
- Cc AO t hp tuyn tnh khi c cng nng lng,
mt e v i xng
- MO t hp c MO lin kt v MO phn lin kt
- Qui tc in e vo MO ging nh AO
6
[ ]
n
ML
+
s
o
x y z
o o o
2 2 2
x y z
o o

2 2 2
* *
x y z
o o

xy xz yz
t t t
* * *
x y z
o o o
*
s
o
6o
1 2 1 2 3 4 5 6
4 ( )
s
c s c o o o o o o o + = + + + + + +
3 4 1 3
3 4 2 4
3 4 5 6
4 ( )
4 ( )
4 ( )
x x
y y
z z
c p c
c p c
c p c
o o o
o o o
o o o
+ = +
+ = +
+ = +
2 2
2 2 2 2
5 6 5 6 1 2 3 4
7 8 1 2 3 4
3 (2 2 )
3 ( )
z z
x y x y
c d c
c d c
o o o o o o o
o o o o o

+ = + +
+ = + + +

0
156 /
o
kJ mol A =
2 6 4 4 *2
s p d d d
o o o t o
3
6
[ ] CoF

265 /
o
kJ mol A =
2 6 4 6
s p d d
o o o t
3
3 6
[ ( ) ] Co NH
+
2 2 2
z x y
xy xz yz
d d
d
d
d d d

A
|
2 2 2
* *
z x y
xy xz yz
t t
t t t

A
|
2 2 2
z x y
x y z
s
o o
o o o
o

|+ |+
|+ |+ |+
|+
2 3
2 2 2 2 2 2
d sp
H OH O H OH OH O
H O
|+ |+ |+ |+ |+ | |+
l l l l l
l
3
2 6
[ ( ) ] Ti H O
+