nh ngha phc cht

Phc chat la hp chat nut

mang tinh the co cha cac ion
phc tap tch ien tch dng hay
am hay phan t trung hoa (phan
t phc) co kha nang ton tai oc
lap trong dung dch
Cau tao phc chat
Phc chat co : cau noi va cau ngoai
Cau noi co: chat tao phc va phoi t
Co phc chat khong co cau ngoai
V du 1: Na
3
[Fe(CN)
6
] co:
*Cau noi : [Fe(CN)
6
]
3-
*Cau ngoai: Na
+
[Fe(CN)
6
]
3-
gom co:
*Chat tao phc: Fe
3+
*Phoi t: CN
-
Cau tao phc chat
V du 2: [Cu(NH
3
)
4
](OH)
2
co:
* Cau noi : [Cu(NH
3
)
4
]
2+
* Cau ngoai : OH
-
[Cu(NH
3
)
4
]
2+
gom co:
* Chat tao phc: Cu
2+
* Phoi t: NH
3
V du 3: Fe(CO)
5
khong co cau ngoai
Fe(CO)
5
gom co:
* Chat tao phc: Fe
* Phoi t: CO
Thuyet lien ket hoa tr
Phc chat c hnh thanh nh lien
ket cong hoa tr cho - nhan gia chat
tao phc va phoi t
+ S phan bo co tnh oi xng cao cua
cac phoi t xung quanh chat tao phc
do trang thai lai hoa cua cac orbital
hoa tr cua chat tao phc.
Thuyet lien ket hoa tr
Phc hexafloridocobaltat(III)
Cu hnh : bat dien
Tnh cht t: Thun t
Mu sc ion phc: xanh l
Thuyet lien ket hoa tr
Phc hexafloridocobaltat(III)
Giai thch theo thuyet lien ket hoa tr:
Thuyet lien ket hoa tr
Phc hexaammincobalt(III)
Cu hnh: bat dien
Tnh cht t: Nghch t
Mu sc ion phc: mau vang
Thuyet lien ket hoa tr
Phc hexaammincobalt(III)
Giai thch theo thuyet lien ket hoa tr:
Thuyet lien ket hoa tr
Phc tetracarbonylnikel(0)
Cu hnh: T din
Tnh cht t : Nghch t
Mau sac: khong mau
Thuyet lien ket hoa tr
Phc tetracarbonylnikel(0)
Giai thch theo thuyet lien ket hoa tr:
Thuyet lien ket hoa tr
Phc tetracloridonikelat(II)
Cu hnh: T din
Tnh cht t: Thun t
Mau sac: Khong mau
Thuyet lien ket hoa tr
Phc tetracloridonikelat(II)
Giai thch theo thuyet lien ket hoa tr:
Thuyet lien ket hoa tr
Phc tetracloridoplatinat(II)
Cu hnh: Hnh vuong
Tnh cht t: Nghch t
Mau sac: o sam
Thuyet lien ket hoa tr
Phc tetracloridoplatinat(II)
Giai thch theo thuyet lien ket hoa tr:
Thuyet lien ket hoa tr
anh gia:
Thuyet lien ket hoa tr giai thch c:
- So phoi tr cua phc
- Cau hnh khong gian cua phc
- Tnh chat t cua phc
Mot so cau hoi khong the giai ap bang
thuyet lien ket hoa tr
V sao cac tren phc co mau, rieng phc
tetracarbonylnikel(0) khong co mau?
V sao cung la phc bat dien cua cobalt(III) ma vi ion
fluoride th khong co s cap oi electron trong ion
Co
3+
, con vi ammoniac th s cap oi electron lai xay
ra?
Cung hoi tng t oi voi nikel: v sao vi phoi t CO
th co s cap oi electron trong nguyen t nikel con vi
phoi t chloride th khong xay ra hien tng nay?
V sao cung loai phoi t, cung so lng phoi t ma
phc tetracloridonikelat(II) co cau hnh t dien, con
phc tetracloridoplatinat(II) co cau hnh hnh vuong?
Thuyet trng tinh the
Noi dung thuyet trng tinh the
Phc chat c tao thanh nh tng
tac tnh ien gia chat tao phc va
phoi t
Tng tc tnh in gia cht to phc v
phi t co the lam thay oi cau truc
electron hoa tr cua chat tao phc.
Khao sat phc bat dien
theo thuyet trng tinh the
Phc phc bat dien [CoF
6
]
3-
, thuan t,
mau xanh l
Ion Co
3+
co cau hnh 3d
6
4s
0
4d
0
5 orbital 3d cua Co
3+
gom:
2 orbital 3d
x2-y2
va 3d
z2
co mat o electron
phan bo theo truc toa o
Khao sat phc bat dien
theo thuyet trng tinh the
Khao sat phc bat dien
theo thuyet trng tinh the
3 orbital 3d
xy
, 3d
yz
va 3d
xz
co mat o electron
phan bo gia cac truc toa o
Khao sat phc bat dien
theo thuyet trng tinh the
Do o cac orbitan 3d
x2-y2
va 3d
z2
tng tc vi cac ion F
-
manh hn cac
orbitan 3d
xy
, 3d
yz
va 3d
xz
. Ket qua 5
orbitan 3d tach thanh hai mc nang
lng d

(e
g
) (cha cac orbitan va ) va
d
c
(t
2g
) (cha cac orbitan 3d
xy
, 3d
yz
va
3d
xz
) theo gian o sau:
Khao sat phc bat dien
theo thuyet trng tinh the
Khao sat phc bat dien
theo thuyet trng tinh the
A
B
= E
d
- E
dc
la thong so tach trng tinh
the phc bat dien
Phc [CoF
6
]
3-
co A
B
= 1,61 eV.
Khi co anh sang chieu qua, electron hap
phu nang lng 1,61eV va nhay t mc
d

(t
2g
) len mc d

(e
g
). Nang lng nay ng
vi bc song mau o, v vay phc
hexafluoridocobaltat(III) co mau xanh da
tri.
Mau sac cua phc - Day hoa quang pho
Bang 1
Bc song b
hap thu
(nm)
Nang lng
(kJ/mol)
Mau cua anh
sang b hap
phu
Mau cua vat
chat
400 435 299 274 Tm Luc vang
435 480 274 249 Xanh tm Vang
480 490 249 244 Lam Da cam
490 500 244 238 Xanh l o
500 560 238 214 Luc Canh sen
560 - 580 214 - 206 Lc Vang Tm
560 595 206 200 Vang Xanh tm
595 605 200 198 Da cam Lam
605 750 198 149 o Xanh l
Mau sac cua phc -Day hoa quang pho
Nh bang 1 t mau sac cua phc suy ra gia
tr A.
T ay rut ra day hoa quang pho cua cac
phoi t cua cung mot loai phc xep theo
giam dan gia tr A :
CO; CN
-
> NO
2
-
> NH
3
> NCS
-
> H
2
O > OH
-
>
> F
-
> SCN
-
> Cl
-
> Br
-
>I
-
Phc spin thap, phc spin cao
ieu kien cap oi electron
Viec ghep oi electron trong mot
orbital tieu ton nang lng (P)
Trong phc bat dien, neu so electron
>3 va <8 th:
Neu A >P th phc la phc spin thap
Neu A < P th phc la phc spin cao
Phc spin thap, phc spin cao
Phc spin thap, phc spin cao
Tnh nang lng on nh trng tinh the va trang
thai t cua hai phc CoF
6
3-
va Co(NH
3
)
6
3+
. Biet
A(kJ/mol) cua
CoF
6
3-
= 155 va Co(NH
3
)
6
3+
= 273,2 va P(kJ/mol) =
250,5
Giai: 1) Xet trang thai t tnh:
Cau hnh electron hoa tr cua Co
3+
la 3d
6
,
* CoF
6
3-
co A < P nen cau hnh Co
3+
la d
c
4
d

2
Phc spin cao, thuan t
Phc spin thap, phc spin cao
Co(NH
3
)
6
3+
co A > P nen cau hnh Co
3+
la d
c
6
Phc spin thap, nghch t.
Phc spin thap, phc spin cao
2) Tnh nang lng on nh trng tinh the
Phc spin cao CoF
6
3-
:
AE = 4(-2/5A) + 23/5A = 2/5A =2/5155 = -62kJ/mol
Phc spin thap Co(NH
3
)
6
3+
:
AE = 6(-2/5A) + 2P = -12/5A +2P = -154,68kJ/mol
Ket luan: Phc spin thap ben hn phc spin cao
Khao sat phc t dien
theo thuyet trng tinh the
phc t dien [Cu(NH
3
)
4
]
2+
, thuan t, mau xanh bien.
Khao sat phc t dien
theo thuyet trng tinh the
V tr cua cac phan t NH
3
so vi ion Cu
2+
tren
hnh cho thay cac phan t ammoniac tac
dung len cac orbital 3d
xy
, 3d
yz
va 3d
xz
(d

)
manh hn tac dung len cac orbital d
x2- y2
va
d
z2
(d

)
Khao sat phc t dien
theo thuyet trng tinh the
Ket qua phan lp 3d tach thanh 2: d

co
nang lng cao hn va d

co nang lng
thap
Khao sat phc t dien
theo thuyet trng tinh the
Phc tetraammin ong(II) co
T
= 1,56V.
Khi co anh sang chieu qua, electron hap phu
nang lng 1,56eV va nhay t mc d

len mc d

.
Nang lng nay ng vi bc song mau o, v vay
phc tetraammin ong(II) co mau xanh nc
bien (blue).

Lu y: V oi vi hai phc co cung chat tao phc

va cung loai phoi t A
T
~ 4/9A
B
nen phc t dien
khong co phc spin thap.
anh gia thuyet trng tinh the
u iem
Giai thch c s phong phu va mau sac cua phc
kim loai chuyen tiep
Tm ra day hoa quang pho
Giai thch c nguyen nhan gay ra t tnh cua phc
(phc spin thap, cao)
Nhc iem
- Giai thch khong thoa ang o ben cua cac phc tao
thanh chu yeu nh lien ket cong hoa tr.
Khong giai thch c ban chat day hoa quang pho
Thuyet orbitan phan t cho phc chat
Noi dung thuyet MO trong phc chat:
Phan t la mot the thong nhat gom cac hat nhan
nguyen t va mot lp vo electron phan t.
Electron trong phan t co mot trang thai rieng c
mo ta bang ham song goi la orbitan phan t.
Xay dng lp vo electron phan t theo phng phap to
hp tuyen tnh cac orbitan nguyen t (LCAO)
Cac AO to hp c vi nhau khi co cung tnh oi xng
va co nang lng gan nhau.
Phc chat c tao thanh co s giam o suy bien cua
cac phan lp cha nhieu orbitan.

Phng phap thiet lap s o nang lng lp

vo electron cua phan t bang cach to hp
tuyen tnh cac ocbitan nguyen t (LCAO
Linear Combination of Atomic Orbitals)
a) Tha nhan rang ch co cac ocbitan nguyen
t (AO) hoa tr la b bien oi ro ret khi tao
thanh phan t do o ch to hp cac AO hoa
tr vi nhau, cac AO con lai chuyen vao
phan t di dang cac ocbitan phan t
khong lien ket (ngha la cac ocbitan nay
khong anh hng en o ben cua phan t
v gi nguyen nang lng co trong nguyen
t).
b) Ch cac AO cua cac nguyen t co tnh oi
xng giong nhau mi to hp vi nhau.
c) S to hp cua cac AO cua cac nguyen t
cang manh khi chung co nang lng cang
gan nhau va chung xen phu nhau cang ln
.
d) Ket qua to hp tuan theo quy tac: aAO
cua nguyen t A to hp vi bAO cua
nguyen t B se tao thanh aMO
lk
, aMO
plk
va (b-a) MO
klk
(b>a) (xem s o hnh sau)
Phng phap LCAO
Phng phap LCAO
Khao sat phc bat dien phoi t khong co
orbital tao lien ket t theo thuyet MO
Xet phc CoF
6
3-
S phan bo cua cac ion F
-
so vi ion
Co
3+
cho tren hnh
Khao sat phc bat dien phoi t khong co
orbital tao lien ket t theo thuyet MO
S to hp theo LCAO:
6 AO 4s , 4p
x
, 4p
y
, 4p
z
, va cua Co
3+
to hp
vi 6 AO 2p
x
cua 6 ion F
-
.
Ket qua tao thanh 12 MO gom:
6 MO o lien ket va 6 MO o phan lien ket
Khao sat phc bat dien phoi t khong
co orbital tao lien ket t theo thuyet MO
V du ve s to hp
S to hp gia 4s cua Co
3+
va 6 AO 2p
x
cua 6 ion
F
-
V du ve s to hp
S to hp gia p
x
cua Co
3+
va 2 AO 2p
x
cua 2 ion F
-
phan bo tren truc x
Khao sat phc bat dien phoi t khong
co orbital tao lien ket t theo thuyet MO
Khao sat phc bat dien phoi t khong
co orbital tao lien ket t theo thuyet MO
V du ve s to hp
S to hp gia 4d
x2-y2
cua Co
3+
va 4 AO 2p
x
cua
4 ion F
-
phan bo tren truc x va truc y
Khao sat phc bat dien phoi t khong
co orbital tao lien ket t theo thuyet MO
Ngoai ra Co
3+
con 3 orbitan 3d
xy
, 3d
yz
va 3d
zx
khong to hp chuyen vao trong
phan t thanh MO t khong lien ket.
Phng phap to hp LCAO cho gian o nang
lng cac phc spin cao CoF
6
3-
va phc spin thap
Co(NH
3
)
6
3+
o khong co lien ket t trang sau :
Nhan xet ve phc da tren gian o cau tao
electron hoa tr phan t
Co(NH
3
)
6
3+
la phc spin thap (Em
s
= 0), nghch t
CoF
6
3-
la phc spin cao (Em
s
= +2), thuan t.
Nang lng tach trng tinh the A = Eo
*
d
- Et
0
dc
Cac phc nay co the co mau do t
0
dc
cha
electron va o
*
d
con trong. (ion Co(NH
3
)
6
3+
:mau
vang; ion CoF
6
3-
:mau xanh l)
Phc spin thap Co(NH
3
)
6
3+
ben hn phc spin cao
CoF
6
3-
do co lien ket o
d
ben hn va tren o
*
d
khong co electron.
Phc bat dien phoi t co orbital tao lien ket t
theo phng phap MO
S xuat hien cac MO t lam thay oi thong so
tach .
Trng hp phoi t nhan t (t-acceptor
ligand):
Cac orbital co the tao lien ket t cua phoi t
to hp vi cac orbital dc cua chat tao phc
lam tang A, lien ket t
0
chuyen thanh t
lk
cha
electron, ket qua lam phc ben vng hn.
Phc bat dien phoi t co orbital tao lien
ket t theo phng phap MO
Trng hp phoi t cho t:(t-donor ligand)
Cac orbital co the tao lien ket t cua phoi
t to hp vi cac orbital dc cua chat tao
phc lam giam A, tuy nhien nh hnh thanh
lien ket t nen phc ben hn trng hp phoi
t yeu khong co orbital tao t. Trong trng
hp nay, th cang nho th lien ket t cang
manh nen phc cang ben.
T cac gian o phc bat dien rut ra cac nhan xet sau:
1)Trong trng hp phc khong co lien ket t, phc cang
ben khi A cang ln v lien ket o(d) cang ben.
2)Trong trng hp phoi t la chat nhan t, phc cang ben
khi A cang ln v MOt lien ket co nang lng cang thap.
3)Trong trng hp phoi t la chat cho t phc cang ben
khi A cang nho v MOt lien ket co nang lng cang
thap.
4)o ln A tang dan theo tnh chat phoi t. Quy luat nay
giai thch c ban chat cua day hoa quang pho:
Phoi t nhan t > phoi t khong tao lien ket t < phoi t cho t
Nhan xet rut ra t cac gian o phc bat dien
Nhan xet rut ra t cac gian o phc bat dien
Nhan xet rut ra t cac gian o phc bat dien
Nhan xet rut ra t cac gian o phc bat dien
Nhan xet 4:
o ln A tang dan theo tnh chat phoi t. Quy luat
nay giai thch c ban chat cua day hoa quang pho:
Phoi t nhan t > phoi t khong tao lien ket t < phoi t
cho t