Ha hc phc cht

Ni dung
1. Nhng khi nim c bn v phc cht
2. Cc thuyt gii thch lin kt trong
phc cht
3. ng hc v c ch ca mt s phn
ng quan trng

Ti liu tham kho
1. C s ha hc phc cht (Trn Th
Bnh)
2. Ha hc v c tp II (Hong Nhm)
3. Phc cht phng php tng hp v
nghin cu cu trc (Trn Th )
Chng I
M u
I.1. Khi nim v phc cht:


2 2
o
t
Cu Cl CuCl +
(1.1)
AgCl + 2NH
3
= AgCl.2NH
3
(1.2)
Phc cht l hp cht c hnh thnh do s ht
cc thnh phn m khng xut hin cc cp
electron mi (Nexraxop)
CuCl
2
hp cht n gin
AgCl.2NH
3
hp cht phn t
Na
+
+ Cl
-
= NaCl c to ra do tng tc tnh in
nh ngha trn cha hon ho
Phc cht l nhng hp cht phn t xc
nh, khi kt hp cc thnh phn ca chng
li th to thnh cc ion phc tp, tch in
dng hoc m, c kh nng tn ti trng
thi tinh th hoc trong dung dch (Grinbe)


Bng phng php ph tia X: tinh th mui n
NaCl l phc cht cao phn t (NaCl)
x
: mi ion
Na
+
c bao quanh i xng bi 6 ion Cl
-
I.2 Thuyt phi tr ca Werner
Ra i ca thuyt phi tr (1892)
- a s cc nguyn t c kh nng th hin 2
dng ha tr: ha tr chnh v ha tr ph.
+ Ha tr chnh - s oxi ha
+ Ha tr ph tng ng s phi tr
- Mi nguyn t u c kh nng bo ha c ha
tr chnh v ph
- Ha tr ph c nh hng theo nhng v tr
nht nh trong khng gian
V d: CoCl
3
.6NH
3

Co
H
3
N
H
3
N
H
3
N
NH
3

NH
3

H
3
N
Cl
Cl
Cl
Co
H
3
N
H
3
N
NH
3

NH
3

H
3
N
Cl
Cl
Cl
(A)
(B)
Co
H
3
N
H
3
N
NH
3

H
3
N
Cl
Cl
Cl
(C)
Co
H
3
N NH
3

H
3
N
Cl
Cl
Cl
(D)
Alfred Werner
CoCl
3

.
6 NH
3

CoCl
3

.
5 NH
3

CoCl
3

.
4 NH
3

CoCl
3

.
3 NH
3

+ HCl
no reaction with NH
3

100%
+ AgNO
3
AgCl (s)
33%
0%
66%
[Co(NH
3
)
6
]
[Co(NH
3
)
5
Cl]
[Co(NH
3
)
4
Cl
2
]
[Co(NH
3
)
3
Cl
3
]
Co c 6 phi t
Cl
3
Cl
2
Cl
Werner xut cu to ca CoCl
3
.6NH
3

Co
H
3
N
NH
3

H
3
N
NH
3

NH
3

H
3
N
Cl
3

Co
3+
: ion (nguyn t trung tm hay cht to
phc)
NH
3
: phi t hay ligan
Trong ngoc: cu phi tr
Ngoi ngoc: cu ngoi
nh ngha hp cht phi tr:
- Phc cht l hp cht phi tr, m phn t ca
n cha ion phc.
- Ion phc bao gm mt nguyn t hay
ion c gi l nhn trung tm, bao
quanh n l cc nguyn t, phn t hay
ion lin kt vi n c gi l ligand hay
phi t. S phi t thng ln hn ho
tr ca nhn trung tm.
I.3. Phn loi phc cht
I.3.1. Phn loi da vo phi t
- Phc hydrat (aqua): phi t l cc phn t H
2
O
nh [Cu(H
2
O)
4
]
2+
, [Mn(H
2
O)
6
]
2+
, [Ni(H
2
O)
6
]
2+
- Phc hydroxo: phi t l nhm OH
-
nh
[Al(OH)
6
]
3-
, [Zn(OH)
4
]
2-
- Phc aminat: phi t l amin
[Co(en)
3
]
3+
; [Co(pn)
3
]
3+

en: H
2
N-CH
2
-CH
2
-NH
2
: etylendiamin
pn: H
3
C-CHNH
2
-CH
2
NH
2
: propylendiamin
- Phc aminacat: phi t l amoniac NH
3
nh:
[Ag(NH
3
)
2
]
+
; [Co(NH
3
)
3
]
3+
; [Ni(NH
3
)
6
]
2+
.
- Phc axido: phi t l gc axit:
[CoF
6
]
3-
, [Fe(CN)
6
]
4-
- Phc cacbonyl: phi t l cacbon oxit CO nh
[Fe(CO)
5
], [Ni(CO)
4
]
- Phc vng: phi t lin kt vi kim loi to
thnh vng
+ Phi t c kh nng to phc vng: en, C
2
O
4
2-
(Ox), EDTA (ethylenediaminetetraacetate)

+ Cng c nhng phi t cha mt s
nguyn t cho, to thnh vng rt ln
ngay c trc khi to phc nh
Porphyrin




- Phc a nhn
- Phc cht c kim: phi t l cc gc
hydrocacbon [Zn(C
2
H
5
)
3
]
-
; [Cr(C
6
H
5
)
6
]
3-


I.2.2. Phn loi theo in tch ca ion phc:
1. Phc cht cation
Cc phi t trung ha phi tr xung quanh ion
trung tm mang in tch dng
V d:
[Zn(NH
3
)
4
]
2+
; [Al(H
2
O)
6
]
3+
; [Co(NH
3
)
6
]
3+
,
[Pt(NH
3
)
4
]
2+
, [Ni(NH
3
)
6
]
2+
2. Phc cht anion
Khi nguyn t trung tm mang in tch
dng phi t l cc anion
[SiF
6
]
2-
, [Zn(OH)
4
]
2-
,
[AlF
6
]
3-
, [Ni(CN)
4
]
2
, [PtCl
4
]
2-

3. Phc cht trung ha
- c to thnh khi cc phn t trung ha
phi t xung quanh nguyn t trung tm l
trung ha
- Khi cc phi t tch in m phi tr xung
quanh ion trung tm tch in dng
[Co(NH
3
)
3
Cl
3
]; [Ni(CO)
4
], [B(NH
3
)F
3
]
I.2.3. Mt s thut ng dng trong phc cht
1. S phi tr:
- L s nguyn t, phn t hoc ion lin kt trc tip
vi nguyn t trung tm
- V d: S phi tr ca ion trung tm Co
3+
, Al
3+

trong cc v d trn u bng 6.
- S phi tr ca ion trung tm khng phi l hng
s, ph thuc vo mt s yu t (bn cht phi t,
bn cht ion to phc, nng , nhit , v.v)
- Mt s ion c s phi tr khng i nh:
+ Co(III), Cr(III), Fe(II), Fe(III), Pt(IV) c spt = 6
+ Pt(II), Au(III) c spt =4
- a s cc ion, spt thay i
+ Cu(II) c spt 2, 4, 6
+ Ni(II), Zn(II) c spt 4, 6
2. Dung lng phi tr:
- Dung lng phi tr (DLPT): l s v tr
phi tr m mt phi t chim c M
n+

V d: OH
-
, Cl
-
, I
-
, F
-
, NH
3
, CN
-
c DLPT
bng 1.
Phi t c dung lng phi tr bng 1 l
phi t n cng.
Phi t c dung lng phi tr ln hn 1 l
phi t a cng
V d: etylendiamin H
2
N-CH
2
-CH
2
-NH
2
c
dung lng phi tr bng 2 th hin trong
phc sau:


Cu
H
2

N
N
H
2

CH
2

CH
2

H
2

N
N
H
2

H
2
C
H
2
C
2+
3. Cch gi tn cc phi t thng gp:
Nu phi t l anion, tn ca anion + ui o
Nu phi t l phn t trung ho, tn ca phn
t
CH
3
COO
-
: axetato H
2
O: aqua
CN
- :
xiano NH
3
: ammin
Cl
-
: cloro CO: cacbonyl
NO
2
- :
nitrito NO: nitrozyl
CO
3
2-
: cacbonato NH
2
CH
2
CH
2
NH
2
:
etylendiamin (en)
OH
- :
hydroxo (NH
2
)
2
CO: cacbamid
SO
3
2-
: sunfito
C
2
O
4
2- :
oxalato
S
2
O
3
2-
: thiosunfato
SCN
-
: thioxianato


4. Cch gi tn cc phc cht:
a. Cation c trc ri mi n anion
[Co(NH
3
)
6
]Cl
3
-
hexaammin coban (III) clorua
[Cr(NH
3
)
6
](NO
3
)
3 -
hexammin crom (III) nitrat
b. Trt t tn phi t
Gi tn phi t m in trc, n phi t trung ha, phi t
dng in, cc phi t c sp xp theo th t t n gin
n phc tp, theo th t a, b, c + thm cc tip u ng:
- di, tri, tetra, trc cc phi t n gin (Cl
-
, Br
-
, NO
2
-
)
- bis, tris, tetrakis,trc cc phi t phc tp nh (en)
c. Tn cng ui ca ion trung tm
- Phc anion: c ui at
- Phc cation hoc phc trung ha khng c ui
d. Bc oxi ha ca ion trung tm
c biu th bng s La M trong ngoc n lin vi M
n+
,
nu s oxi ha m hoc =0 th t du m trc s La M,
hoc ghi s 0

V d:
[PtClNO
2
(NH
3
)
4
]SO
4
:
cloronitrotetraammmin platin (IV) sunfat
K
3
[Al(C
2
O
4
)
3
]: Kalitrioxalatoaluminat (III)
[CoCl
2
(en)
2
]Cl: Diclorobis(en) coban(III) clorua
Chng II
Lin kt trong phc cht
II.1. Thuyt lin kt tnh in ca Kossel
1. Ni dung:
- Lin kt trong phc cht c to ra l
do lc ht tnh in gia nguyn t trung
tm vi cc phi t
- Kossel tnh nng lng to thnh trong
phc cht, vi gi thit: cc ion l nhng
qu cu khng b bin dng, c bn knh
nh nhau, tng tc vi nhau theo nh
lut Coulomb
V d 1: S to thnh ion [Ag(CN)
2
-
]
CN
-

CN
-

Ag
+

Lc ht gia ion Ag
+
v CN
-
: f
h
= e
2
/r
2
Lc y gia cc ion CN
-
: f

= e
2
/4r
2
r - khong cch gia tm ca cc ion
- bn ca phc cht ph thuc vo t l
gia lc ht v lc y, c trng bng
hng s S
- Khi ion trung tm tch in (+1) to phc
vi cc ion (-1), ng tnh c hng s
chn S v gi thit chng c cc cu hnh
khng gian khc nhau.
S phi tr
n
Hng s chn
S
Cu hnh khng gian
ca phc cht
2 0,25 ng thng
3 0,58 Tam gic u
4 0,92 T din u
4 0,96 Vung phng
5 1,38 Nm cnh u
6 1,66 Bt din u
Bng 1. Hng s chn v cu hnh khng gian ca
mt s phc cht c s phi tr khc nhau
* Nhn xt:
Ion trung tm in tch (+1) phc bn
nht c spt 2, 3
Phc c spt cao khng bn (do lc y
mnh hn lc ht)
spt 4 rt t gp nhng v mt nng
lng th cu hnh t din bn hn
vung phng
2. Nng lng to thnh ca phc cht
- Khi ion trung tm c in tch khc +1
- Phi t c in tch -1
- Nng lng thot ra khi to thnh mt
phn t phc cht c tnh theo h thc:


2
( )
e
U n Z S
r
=
U ph thuc vo s phi tr n v cch sp xp trong
khng gian ca cc phi t
Nu r= const th U s t l vi n(Z-S)
Bng 2. Cc gi tr ca n(Z-S) khi n v Z thay i

n
Z
1 2 3 4 5 6
1 1,00 1,50 1,26 0,30
2 2,99 3,50 4,26 4,30 3,12 2,04
3 3,00 5,50 7,26 8,32 8,12 8,04
4 4,00 7,50 7,26 12,32 13,12 14,04
Nhn xt:
- Khi s phi tr n tng, tr s n(Z-S) tng, nng lng
U tng qua cc i ri gim
- Cc ion in tch (+1), vi spt 2 c xc sut ln nht,
ri n spt 3
V d: Ion Ag (I), Cu(I), Au(I) to c cc phc cht
dng M[AgX
2
], [CuCl
2
]
-
; [Au(CN)
2
-
]
- Cc ion in tch (+2) nh Zn
2+
, Cd
2+
, Hg
2+
, Cu
2+
, Pt
2+
c spt 4 l thun li nht, ri mi n 3
V d: [CuCl
4
]
2-
; [Zn(OH)
4
]
2-
; [PtCl
4
]
2-
; [HgI
4
]
2-
;
[CuCl
3
]
-

- Cc ion c in tch (+3), spt thng gp l 4 v 6,
nh: [BF
4
]
-
; [CoF
6
]
3-
;[AuCl
4
]
-
- Cc ion c in tch (+4) th spt ph bin l 6
u nhc im:
- Cho php gii thch c spt ca a s
cc ion kim loi, xc nh spt c
trng, cu hnh khng gian
- Khng cho php gii thch tnh mu v
t tnh ca phc cht
II.2. Cc thuyt hin i gii thch bn cht
lin kt trong phc cht
- Thuyt lin kt ha tr
- Thuyt trng tinh th
- Thuyt obitan phn t MO
II.2.1 Thuyt lin kt ho tr gii thch lin kt
ho hc trong phc cht
Nguyn tc ca phng php:
Lin kt to thnh trong phc cht l lin kt
cho-nhn gia cp e t do ca phi t v obitan
trng ca nhn trung tm. Mi lin kt cho-nhn
ng vi mt v tr phi tr (mt lin kt o).
Cc obitan trng phi l nhng obitan
lai ho. Nhn trung tm l cht nhn cp
e. Phi t l cht cho cp e

V d 1: S to thnh ion phc [Co(NH
3
)
6
]
3+

+ T ion Co
3+
v 6 phn t NH
3

+ To thnh cation phc hnh bt din do 6 lin
kt cho-nhn gia cc cp e t do ca cc
phn t NH
3

+ Trong ion Co
3+
c s lai ho d
2
sp
3


Co
3+
3d
6
4s
4p
NH
3
NH
3
NH
3
NH
3
NH
3
NH
3
d
2
sp
3
Co
3+
- d
2
sp
3
l s lai ho trong
- Loi phc ny cha t hoc khng cha
cc e c thn so vi nhn trung tm
trng thi t do
- Phc cht spin ghp cp (phc cht spin thp
hoc phc cht obitan trong)
- Ion [Co(NH
3
)
6
]
3+
khng c e c thn,
Thc nghim xc nhn ion [Co(NH
3
)
6
]
3+
c tnh
nghch t
V d 2: s hnh thnh ion phc [CoF
6
]
3-
- Trong trng hp ny nhn trung
tm l Co
3+
c lai ho sp
3
d
2
, tc l cc
AO- 3d lp trong khng tham gia lai
ho
- Xy ra s lai ho ca AO-4s, vi 3AO- 4p v
2AO- 4d. y l s lai ho ngoi.

3d
6
4s
4p 4d
sp
3
d
2
- sp
3
d
2
l s lai ho ngoi
- Phc cht to thnh c gi l
phc cht obitan ngoi (phc cht
spin cha ghp cp hoc phc cht
spin t do).
- Phc cht ny vn gi c s e t
do ca nhn trung tm, c tnh thun
t.
- Kt qu o momen t cho thy ion
[CoF
6
]
3-
c 4 e c thn

Mt s dng lai ho obitan thng gp
v cu trc hnh hc ca phc cht

S phi
tr
Dng lai
ho
Cu hnh
ca phc
cht
V d
2 sp Thng [Cu(NH
3
)
2
]
+
, [CuCl
2
]
-
[Ag(NH
3
)
2
]
+
, [Ag(CN)
2
]
-
,
4 sp
3
T din [Zn(NH
3
)
4
]
2+
, [ZnCl
4
]
2-
,
[BF
4
]
-
, [Be(OH)
4
]
2-,
[Hg(CN)
4
]
2-
4 dsp
2
Vung phng [PtCl
4
]
2-
, [Ni(CN)
4
]
2-
,
[Cu(NH
3
)
4
]
2+

6 d
2
sp
3
Bt din [Co(NH
3
)
6
]
3+
, [Fe(CN)
6
]
3-
6 sp
3
d
2
Bt din
[CoF
6
]
3-
, [PtCl
6
]
2-
,
[Al(H
2
O)
2
(OH)
4
]
-
, [SnCl
6
]
2-
,
L M L


Thng
T din u
Vung
phng
Bt din
2. u nhc im
- n gin, d hiu, cho php gii
thch nh tnh lin kt ca phc
cht, gii thch tnh thun t v
nghch t.
- Khng gii thch c mt s tnh
cht ca phc cht nh tnh cng
hng t, tnh d hng, tnh cht
quang hc, mu ca cc phc cht
- Nhng thnh cng, tn ti ca n c
p dng, b sung v pht trin trong
thuyt trng tinh th v thuyt MO
II.2.2. Thuyt trng tinh th
- Thuyt trng tinh th do hai nh
Bc hc Vt l Bethe v V. Vleck
ra nm 1933 gii thch
tnh cht ca cc cht dng tinh
th.
- 1950 n mi c p dng vo
phc cht ca cc kim loi
chuyn tip
Nguyn tc c bn ca Thuyt trng tinh
th gm cc im sau y:
Phc cht c to thnh v bn l nh vo
lc ht tnh in gia nhn trung tm v
phi t
Khi xt ion trung tm c ch n cu trc
electron chi tit ca n; cc phi t c coi l
khng c cu trc, l nhng in tch im
(hoc lng cc im) to nn trng tnh in
bn ngoi i vi ion trung tm (trng phi
t).
Cc phi t nm xung quanh ion trung tm
trn cc nh ca hnh a din, to nn nhng
phc cht c cu trc i xng nht nh.
Ni dung:
Xt s tch mc nng lng ca
cc obitan d ca ion trung tm M
n+
di tc dng ca trng phi t
Cc phc cht c tnh i xng khc
nhau s tch cc obitan d s khc
nhau
1. Phc bt din:
Xt cu trc hnh hc ca ion phc tm
mt:


z
y
x
L
1

L
2

L
3

L
4

L
6

L
5

A
Nguyn t trung tm M
n+
c 5 obitan ho tr
d, trng thi t do cc obitan ny c nng l-
ng bng nhau (s suy bin bc 5)
Khi cc phi t tin li gn to lin kt
th xut hin tng tc y gia cc in tch m
ca phi t vi electron d ca nhn trung
tm, cn tr in electron vo cc obitan d.
Tng tc gia phi t vi nhn khng ging
nhau nn nng lung ca cc obitan ny tng
ln khng u. Dn n s tch mc nng
lng ca cc obitan d thnh hai nhm.

L
1

L
2

L
3

dx
2
-y
2


L
6

L
1

L
2

L
3

L
4

L
5

dz
2


L
1

L
3

L
2

dxy

L
5

L
3

L
4

dzy
L
4
L
4
L
6

L
5

L
1

L
6

L
3


L
2

dzx
+ Nhm gm 2AO-d: dz
2
v dx
2
-y
2
(k
hiu e
g
) hng trc tip n cc phi
t nn, chu tng tc y mnh hn,
nng lng ca 2AO ny tng ln
mnh.
+ Nhm gm 3AO-d d
xy
, d
xz
, d
zy
(k
hiu t
2g
) nh hng gia cc phi t,
tng tc gia cc AO ny vi cc phi
t km hn nn nng lng thp hn
+ Di tc dng ca in trng su
phi t cc obitan d t suy bin bc 5
b tch thnh hai nhm: e
g
suy bin
bc 2 v t
2g
suy bin bc 3


S tch nng lng ca cc
obitan d trong trng tinh
th





E
2
E
1
E
0
Nng lng trung bnh
ca cc OA- d


2/5
o
d
Z2
d
x2-y2
d
xy d
xz
d
yz
3/5
o
e
g
t
2g
S tch mc nng lng ca cc obitan d trong
trng bt din
2. Phc t din:

Z
X
Y
Cc phi t khng nm trn cc trc m nm
trong khong khng gian gia cc trc
Trong ion phc bn mt:
3AO-d: d
xy
, d
xz
, d
yz

c cc nhnh hng ti gn
cc phi t hn, chu tc dng y ln hn
nn nng lng tng ln mnh hn
2AO-d: d
Z2
, d
x2-y2

c cc nhnh xa cc phi
t hn nn chu tc dng y yu hn,
nng lng thp hn
Kt qu di tc dng in trng ca 4 phi
t 5AO-d ng nng lng ca ion t do M
n+
b phn tch thnh 2 mc:
+ t
2g

gm 3AO d
xy
, d
xz
, d
yz

+ e
g

gm 2AO d
Z2
, d
x2-y2




S tch nng lng ca cc
obitan d trong trng t
din





E
2
E
1
E
0
Nng lng trung bnh
ca cc OA- d


0,4
o
d
Z2 d
x2-y2
d
xy
d
xz
d
yz
0,6
o
t
2g
e
g
Khi tnh i xng ca trng gim cc nhm t
2g
v e
g
tip
tc b phn tch v mc suy bin ca chng gim i hoc
bin mt
3. Phc vung phng:

X
Y
Z
L
1
L
2
L
3
L
4
L
6
L
5
Khi 2 phi t L
5
, L
6

ri ra
xa hn nhn th phc bt
din tr thnh vung
phng d
x2-y2
, d
xy
tip tc
tng, cn d
Z2
, d
zx
, d
yz
tip tc
gim
Hai phi t v tr
trans (L
5
, L
6
) ko dn
ra xa theo trc Z
phc cht bt din
lch
L
5
, L
6
s xa nhn, cc
phi t L
1
, L
2
, L
3
, L
4
trn
mt phng c xu hng
co li
e
g
: d
x2-y2
v d
Z2
b
phn tch: d
x2-y2
c nng
lng tng ln, cn d
Z2
gim
xung.
t
2g
: d
xy
tng ln cn
d
zx
, d
zy
gim xung

Bt din
lch
Vung
phng
d
x2-y2
d
Z2
d
xy
d
xz
d
yz
d
x2-y2
d
Z2
A
o
d
xy
d
XZ
d
yz
Bt din
u
d
x2-y2
d
Z2
d
xy
d
XZ
d
YZ
Hiu ng Jan- Tel:
- Trong phc bt din, khi 2 phi t v tr
trans (L
5
, L
6
), dch chuyn ra xa hay gn ion
trung tm so vi cc phi t khc, phc bt
din b bin dng kiu t phng (bt din
lch)
- S bin dng kiu t phng ca phc cht
bt din l biu hin ca hiu ng Jan- tel
- Trng thi electron suy bin ca mt phn t
khng thng hng l khng bn, phn t s
bin dng hnh hc gim tnh i xng v
suy bin
V d:
Xt phc bt din ca Cu
2+
(d
9
)
Cu hnh ca Cu
2+
trong phc bt din: (t
2g
6
e
g
3
)
Trn e
g
c 3 electron nn c 2 cch phn b
electron:

2 2 2
2 2 2
2 1
1 2
z x y
z x y
d d
d d

Hai cu hnh ny c cng mt mc nng lng nn

trng thi electron ca Cu
2+
trong phc bt din l
suy bin bc 2

- Trng thi electron khng bn, nn phc bt
din ca Cu
2+
phi bin dng hai cu hnh
khc nhau
+ Cu hnh:


2 2 2
2 1
z x y
d d

V thiu 1 e nn cc phi t trong mt phng xy b chn
t hn v c ht li gn nhn mnh hn so vi phi
t trn z
Cc phi t trn trc Z b y ra xa ion kim loi
Do , 4 lin kt trong mt phng xy ngn hn 2 lin
kt theo trc Z.
Phc cht b bin dng kiu t phng, phc bt din
tr thnh bt din thun v suy bin gim i
+ Cu hnh:

2 2 2
1 2
z x y
d d

Cc phi t trong mt phng xy b y ra xa so
vi nhn
Cc phi t trn z s ht li gn nhn hn
2 lin kt trn trc z s ngn i, cn 4 lin kt trn
mt phng xy di ra
Phc bt din b dt li theo trc z
















S lch cu hnh khi tch e dx
2
-y
2
v dz
2
- Thc t t gp kiu lch th hai (lch do nn
theo trc z)
- S lch ko di cc lin kt dc theo trc z
(bt din thun) thng gp hn
- S lch theo kiu t phng qu ln th hai
phi t trans trn z c th b mt i, khi
phc cht tr thnh vung phng
- Bt din lch t phng v vung phng cc
mc t
2g
v e
g
u gim suy bin, h tr nn
bn hn
- nh l ny c ngha thc t to ln, v n
cho php chng ta hiu c cu to nhiu
phc kim loi chuyn tip
Tuy nhin

khi p dng cn lu nhng c im
sau y:
1. nh l xc nhn s bin dng hnh hc ca h
suy bin, nhng khng ni g v c im v
ln ca s bin dng
2. Cn phi tnh nng lng ca ton b phc
cht c th d on c c im v ln
ca s bin dng. Tuy nhin, s tnh ton rt kh
nn t khi thc hin c. Cu hnh cn bng l
cn hnh ng vi nng lng nh nht.
V d 1: Xt cu hnh ca phc cht Cu
2+
(h
d
9
)

- S lch ko di theo trc z thng gp hn
-
1
l thng s tch i vi mc e
g
v
2
l
thng s tch- mc t
2g

- Thc t
2
<
1
<
o

- Trong h Cu
2+
khng c s di nng lng do
tch mc t
2g

2
2
2
4 2
3 3
o
o +
- Nhng i vi mc e
g
, nng lng di ra l:

1
1 1
1 1
2 1
2 2 2
o
o o
| |
+ =
|
\ .
- Nng lng ny l nng lng lm bn
bi hiu ng Jan-Tel
- V l nguyn nhn lm bin dng
cu hnh hnh hc ca phc cht
Ch :
- Cu hnh t
2g
6
e
g
1
v t
2g
6
e
g
3
s bin dng
hnh bt din lm cho phc cht bn
- Cu hnh t
2g
6
, t
2g
6
e
g
2
v t
2g
6
e
g
4
phc
cht khng b bin dng
- Cu hnh t
2g
3
e
g
1
cng b bin dng
4. Nng lng tch
- S tch mc nng lng ca cc obitan d l do
tng tc ca cc phi t vi cc electron d trn
obitan
- Thng s tch (nng lng tch) l i lng c
trng cho s tch, k hiu
- Phc bt din
o

v phc t din
t

- Cng thc: W
s
= (0,4n
1
- 0,6n
2
)A
o
Trong : n
1
- s electron trn cc obitan t
2g
n
2
- s electron trn obitan e
g
n v l s sng (cm
-1
)
5. Cc yu t nh hng n thng s tch
Bn cht ca phi t v ion M
n+
v cu hnh
ca phc cht
* Bn cht phi t:
+ Phi t c m in ln, kch thc nh l
cng d gn ion kim loi v ln
V d: Thc nghim cho thy theo dy F- Cl
-
- Br

- I
-
th gim dn
+ Phi t c 1 cp e t do (NH
3
) s d tin gn
ion M
n+
hn l phi t c 2 hay nhiu hn
cp e t do (H
2
O)


* Bn cht ca ion trung tm:
Trng thi oxi ha, cu hnh electron v kch
thc ca ion trung tm
+ S oxi ha ca ion trung tm cng cao th
cng ln (s ht gia ion M
n+
vi phi t cng
mnh)
[Mn(H
2
O)
6
]
2+
A
o
= 7800; [Mn(H
2
O)
6
]
3+
A
o
=
13700
[Fe(H
2
O)
6
]
2+
A
o
= 10400 m
-1
; [Fe(H
2
O)
6
]
3+
A
o
=
21000 m
-1

+ Ion trung tm c kch thc cng ln, obitan
ca n cng d b bin dng, kh nng to
phc cng cao
ca phc cha cc electron 5d ln hn so
vi phc cha electron 3d
* Cu hnh electron ca phc cht:
- Vi phc bt din s trn t
2g
cng ln, lc
y gia chng cng mnh, nng lng mc
cng cao,
o
nh
- S e trn mc e
g
cng ln th nng lng ca
mc cng cao,
o
cao
V d:
Theo dy d
1
- d
2
- d
3
thng s tch gim
v tng mnh d
4

6. Cu hnh electron ca phc cht
- S phn b electron trn cc obitan d tun
theo cc nguyn l v quy tc nh nguyn
t
- Tuy nhin cn ph thuc vo mi tng quan
gia P nng lng ghp i v
- C ba trng hp khc nhau:
1. d
1,2,3
c mt cch in duy nht
2. d
4,5,6,7
s c hai cch in khc
nhau
3. d
8,9,10
c mt cch in duy nht

d
1

d
2

d
3
d
4

Phn b electron vo d orbitals
Strong field Weak field
Strong field Weak field
d
4

Strong field =
Low spin
(2 unpaired)
Weak field =
High spin
(4 unpaired)
H < A
o
H > A
o

Notes: the pairing energy, P, is made up of two parts. 1) Coulombic
repulsion energy caused by having two electrons in same orbital
S phn b electron vo obitan d
Placing electrons in d orbitals
1 u.e. 5 u.e.
d
5

0 u.e. 4 u.e.
d
6

1 u.e. 3 u.e.
d
7

2 u.e.
2 u.e.
d
8

1 u.e. 1 u.e.
d
9

0 u.e. 0 u.e.
d
10

- Cc phi t mnh thng to ra cc
phc spin thp, cn cc phi t
yu thng to ra cc phc spin cao.


8. Mt s h qu ca s tch trng phi t
S hp th nh sng: mu ca cht l do
s hp th nh sng nhn thy
Khi cht hp th hon ton nh sng
cht s c mu en.
Khi cht khng hp th nh sng cht
trong sut hoc c mu trng
Cht hp th mt phn nh sng, phn
khng b hp th truyn qua cht gy ra
mu ph tr
V d: Khi nh sng i qua mt cht, b
hp th mu , th mu quan st c l
mu lc
Ph hp th: l ng cong biu din s
bin i ca hp th nh sng theo bc
sng

-

8.1. Thnh cng ln nht ca thuyt trng
tinh th l gii thch mu ca cc phc cht
kim loi chuyn tip
V d:
- [Ti(H
2
O)
6
]
3+
c mu tm do hp th cc
i bc sng = 500nm
- Ion phc hp th nh sng vng, cn cho
nh sng , xanh i qua gy ra mu
tm




e
g
t
2g
h
(=500nm)
[Ti(H
2
O)
6
]
3+
A
o
= 242,8
KJ.mol
-1
A A o
N
hC
N h . .

= = A
Ch :
Xc nh
o
i vi cc phc cht c s e electron
nhiu hn 1 rt phc tp, v khng nhng ph thuc
vo nng lng obitan m cn ph thuc nng lng
ca tng tc y gia cc electron
Da vo cc gi tr
o

xc nh dy ph ha hc
ca cc phi t nh sau:

I
-
< Br
-
< Cl
-
< OH
-
< F
-
H
2
O<NCS
-

<NH
3
<en<NO
2
-
< CO, CN
-
Trng phi t yu

Trng pt trung
bnh


Trng pt mnh


Dy ph ha hc ca cc ion kim loi c sp
xp theo trt t nh sau:
Mn
2+
<V
2+
<Co
2+
<Fe
2+
<Ni
2+
<Fe
3+
<Co
3+
<Mn
4+
<Mo
3+
<Rh
3+
< Ru
3+
<Pd
4+
<Ir
3+
<Pt
4+
8.2. T tnh ca phc cht
Da vo tc dng ca t trng, chia lm hai loi:
phc cht nghch t v phc cht thun t
trng thi c bn cu hnh electron ca cc phc
kim loi chuyn tip c cc e c thn, ngi ta
dng phng php o momen t nhn ra cu
hnh
+ Momen t ca phc vi s lng t spin tng cng
S c xc nh bng h thc:


2. ( 2).
B
S S = +
Do mi e c thn c s lng t spin l nn
S= n/2, vi n l s electron c thn
( 2).
B
n n = +
Bng 1. Momen t spin thun ty ca cc
phc cht dy 3d

Ion n S /
B
L thuyt Thc nghim
Ti
3+
1 1/2 1,73 1,7-1,8
V
3+
2 1 2,83 2,7-2,9
Cr
3+
3 3/2 3,78 3,8
Mn
2+
4 2 4,9 4,8-4,9
Fe
3+
5 5/2 5,92 5,3