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:

tr
Phc hexaammincobalt(III)
Cu hnh: bat dien
Tnh cht t: Nghch t
Mu sc ion phc: mau vang

tr
Phc hexaammincobalt(III)
Giai thch theo thuyet lien ket
hoa tr:

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 Co3+, 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.

C s ca s to phc:
Phc cht tn ti c l nh lc ht tnh in

gia ion trung tm M v cc phi t L

Trong phc cht:

M c cu trc e, v b nh hng bi in

trng ca cc L

Cc L: cc in tch im khng c cu

trc, phn b i xng quanh ion trung

tm, l ngun cung cp trng tnh in.

Di tc dng y tnh in ca cc L, cc

phn lp d, f ca M b tch ra thnh cc

phn lp nh hn.

Phc cht c m t bng cc nh lut ca

c hc lng t.

Xt cc phc cht ca nguyn

Cc AO (n - 1)d: d , d , d (d ), d
, d (d )
td
xy

yz

zx

x2 y2

z2

tham gia to lk vi cc L.
trng thi c bn cc AO nd c nng lng
nh nhau: End
Khi c cc L bao quanh th ty cch phi tr

ca cc phi t m cc AO d b nh hng khc

nhau v tr thnh c nng lng khc nhau:
S phi tr i xng cu: cc AO nd khng suy bin

nhng End tng ln

S phi tr bt din:

Ed < End (-0,4bd)

Ed > End (+0,6bd)

S phi tr t din: Ed > End (+0,4td)

Ed < End (-0,6td)

Thng s tch trng tinh th

Thng s tch trng tinh th ph thuc vo:

Cu hnh phc cht:

4
t din
9

bt din

Bn cht nguyn t trung tm M v phi t L:

tng dn theo dy quang ph ha hc:

Phi t trng yu: I- < Br- < S2- < SCN- < Cl- < F- <

OH-

< ONO- < C2O42- < H2O

Phi t trng trung bnh:

NCS- < CH3CN < NH3

< en (ethylenediamine) < bipy(2,2-bipyridine) <

phen (1,10-phenanthroline)
Phi t trng mnh: < phofpho < CN - < CO.

S phn b electron trn cc

S phn b e trn cc AO d ca M trong phc
AO d

cht cng tun theo cc nguyn l v quy tc

ca CHLT v c bit ph thuc vo thng s
tch
Bt din trng yu ( < P): to phc spin cao
Bt din trng mnh ( > P): to phc spin thp
i vi trng t din: ch c trng yu nn lun

to phc spin thp

V d
S electron d
d4
d5
d6
d7

Phc bt din
spin cao

Phc bt din
spin thp

Kt lun: Thuyt trng tinh

u iem
th
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)
C th d on tnh bn ca cc phc cht da vo
ga tr nng lng n nh trng tinh th.
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

Nng lng n nh trng tinh

Phc bt din spin cao:
th

E n d bd n d bd
5

Phc bt din spin thp:

E n d bd n d bd mP
5

Phc t din:

E n d td n d td
5

AO d
d

Cc AO nd trong trng bt din

Cc AO nd trong trng bt din

Trng bt din

Cc AO nd trong trng t din

Trng t din

Cc AO nd trong trng t din

MAU CUA PHC CHAT

Do co hien tng tach mc nang

lng nen khi e nhay t mc nang

lng thap len mc nang lng cao
se hap thu nang lng (nam trong
vung kha kien) lam cho phc chat
thng co mau sac.

E = h = hc/ = 1240 (eV)/ (nm)

Neu nam trong vung kha kien (400

700 nm), ta co E t 3.1 en 1.8 eV.

Neu E < 1.8 eV th anh sang b hap
thu nam trong vung hong ngoai, khong
thay c (tng t cho vung t
ngoai).

BANG MAU HAP THU CUA

CAC
PHC
Bc song
E (kJ/mol)
Mau cua
Mau cua
b hap thu
(nm)

bc song
b hap thu

phc chat

400 435

229
274

Tm

Luc-Vang

435 480

274
249

Lam (blue)

Vang

480 490

249
244

Lam-Luc
nhat

Cam

490 500

244
238

Luc-Lam
nhat

500 560

238
214

Luc
(green)

o ta

560 580

214
206

Luc-Vang

Tm

Crystal field d orbital splitting

diagrams

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
a) Tha nhan rang ch co cac ocbitan
nguyen
t (LCAO Linear
nguyen t (AO) hoa tr la b bien oi
Combination
ofthanh
Atomic
Orbitals)
ro ret khi tao
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).

Phng phap LCAO

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 , aMOplk
va (b-a) MOklk (b>a) (xem s o hnh sau)

Phng phap LCAO

Khao sat phc bat dien

phoi t khong co orbital tao
lien ket theo thuyet MO

Xet phc CoF63-

S phan bo cua cac ion F- so vi

ion Co3+cho tren hnh

Khao sat phc bat dien

phoi t khong co orbital tao
lien ket theo thuyet MO
S to hp theo LCAO:
6 AO 4s , 4px , 4py , 4pz, va cua Co3+
to hp vi 6 AO 2px cua 6 ion F-.
Ket qua tao thanh 12 MO gom:
6 MO lien ket va 6 MO phan
lien ket

phoi t khong co orbital

tao lien ket theo thuyet
MO
V du ve s to hp
S to hp gia 4s cua Co3+ va 6 AO
2px cua 6 ion F-

phoi t khong co orbital

tao lien ket theo thuyet
MO
V du ve s to hp
S to hp gia px cua Co3+ va 2
AO 2px cua 2 ion F- phan bo tren
truc x

phoi t khong co orbital

tao lien ket theo thuyet
MO
V du ve s to hp
S to hp gia 4dx2-y2 cua Co3+ va 4 AO
2px 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 theo thuyet
MO
Ngoai ra Co3+ con 3 orbitan 3dxy, 3dyz
va 3dzx khong to hp chuyen vao
trong phan t thanh MO khong lien
ket.
Phng phap to hp LCAO cho gian o
nang lng cac phc spin cao CoF 63- va phc
spin thap Co(NH3)63+o khong co lien ket
trang sau :

Nhan xet ve phc da tren

gian o cau tao electron hoa
tr phan t
Co(NH3)63+ la phc spin thap (ms = 0), nghch

t
CoF63- la phc spin cao (ms = +2), thuan t.
Nang lng tach trng tinh the = E *d -

E 0d
Cac phc nay co the co mau do 0d cha

electron va *d con trong. (ion Co(NH3)63+

:mau vang; ion CoF63- :mau xanh l)

Phc spin thap Co(NH3)63+ ben hn phc spin

cao CoF63- do co lien ket d ben hn va tren

*d khong co electron.

Phc bat dien phoi t co

orbital tao lien ket theo
phng phap MO

S xuat hien cac MO lam thay oi

thong so tach .
Trng hp phoi t nhan (acceptor ligand):
Cac orbital co the tao lien ket
cua phoi t to hp vi cac orbital d
cua chat tao phc lam tang , lien
ket 0 chuyen thanh lk cha electron,
ket qua lam phc ben vng hn.

Phc bat dien phoi t co

orbital tao lien ket theo
phng phap MO
Trng hp phoi t cho :(-donor

ligand)
Cac orbital co the tao lien ket
cua phoi t to hp vi cac orbital d
cua chat tao phc lam giam , tuy
nhien nh hnh thanh lien ket nen
phc ben hn trng hp phoi t
yeu khong co orbital tao . Trong
trng hp nay, th cang nho th
lien ket 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 ,
phc cang ben khi cang ln v lien ket
(d) cang ben.
2)Trong trng hp phoi t la chat nhan ,
phc cang ben khi cang ln v MO lien ket
co nang lng cang thap.
3)Trong trng hp phoi t la chat cho phc
cang ben khi cang nho v MO lien ket co
nang lng cang thap.
4)o ln tang dan theo tnh chat phoi t.
Quy luat nay giai thch c ban chat cua
day hoa quang pho:
Phoi t nhan > phoi t khong tao lien ket <
phoi t cho

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 tang dan theo tnh chat

phoi t. Quy luat nay giai thch c
ban chat cua day hoa quang pho:
Phoi t nhan > phoi t khong tao
lien ket < phoi t cho