Lun im c bn:

Phc cht tn ti mt cch bn vng l do tng tc tnh in gia ion trung tm v cc phi t phn b i xng xung quanh

Ch xt n cu hnh electron chi tit ca ion trung tm v xt n bin i do in trng ca cc phi t gy nn. Ch coi phi t nh cc in tch im to nn trng tnh in bn ngoi. Phi t nm xung quanh ion trung tm trn cc nh ca hnh a din nn phc cht c s i xng nht nh.

Phc cht bt din

x y

d z2

d x2 y 2

d xy

d xz

d yz

S o phan bo mat o electron cua 5 orbitan d tng ng vi 6 ien tch am tap trung cac nh cua hnh bat dien

E
3 o 5
2 o 5

Ion t do

Ion trong trng i xng cu

Trong trng bt din

 Phc cht t din

E
2 td 5 3 td 5

td

Ion t do

Ion trong trng i xng cu

Trong trng t din

u im: Cho php gii thch mu sc v t tnh ca cc cht. Nhc im: Khng gii thch bn cht ca lin kt S phn b mt e trong phc cht khng cho php xc nh 1 cch nh lng chnh xc cc c trng nng lng v cc c trng khc Khng gii thch c dy ha quang ph.

QUAN IM CA THUYT MO
V PHC CHT
Phc cht c xem nh mt h thng CHLT thng nht trong cc nguyn t ring bit v phn t mt nhng c tnh ring ca mnh Cc e ha tr ca h c phn b trn cc obital phn t (MO) nhiu tm. Chuyn ng ca mi e c xc nh bi v tr ca cc ht nhn v c im chuyn ng ca cc e cn li.

S dng cc phng php gn ng (phng php gn ng 1 e)

Phng php gn ng cho rng mi chuyn ng c lp trong trng hiu ng trung bnh c to bi tt c cc ht nhn v cc e trung bnh khc.

XY DNG CC MO
Xy dng MO trn c s cc AO ca cht to phc v ca cc phi t. My e xen ph cc i v c li v mt nng lng hnh thnh MO lin kt ( ) Xen ph m ca cc my e v s tng nng lng ca h hnh thnh MO phn lin kt ( *) Nu AO ca cht to phc khng xen ph hoc hu nh khng xen ph vi cc obital ca cc phi t nng lng chng khng bin i cc AO chuyn thnh MO vi mc nng lng (MO khng lin kt)

Phc bt din khng c lin kt

Phc bt din

Phc bt din c lin kt b sung

 PHC BT DIN KHNG C LIN KT

Gi thuyt: Cc phi t ch s dng cc obital phn b theo tr c hng n ion trung tm xen ph vi cc obital ca cht to phc to thnh 1 lin kt.
iu kin i xng

Chng khng th to thnh lin kt , trong trng hp ny phc ch to lin kt

IU KIN TO THNH LIN KT

to thnh lin kt, cht to phc (nguyn t d) s dng cc AO ha tr ns, np ca lp e ngoi cng v (n-1)d ca lp e k ngoi cng. S xen ph gia cc obital ca cht to phc v phi t cng ch xy ra khi c nng lng gn nh nhau v tng ng vi s nh hng khng gian ca chng

Trong s 9 obital ha tr ca cht to phc: 6 obital d z2 , dx2 y2 ,s, px, py, pz c kh nng tham gia cc lin kt 3 obital dxy, dxz, dyz thch hp trong vic hnh thnh lin kt vi cc phi t.

Obital ns c tnh i xng cu c kh nng xen ph vi c 6 phi t phn b dc theo cc trc x, y, z

z y +

2 MO 7 tm

s v s*

Mi AO p ca cht to phc s xen ph vi 2 obital ca phi t phn b trn 2 trc tng ng 2 MO 3 tm

p v

* p

3 MO lin kt px , py , pz
C 3 AO p
z y

6 MO

3 MO phn lin kt * ,* ,* px py pz

px

z y

pY
z

pZ

Vi cc AO d: Ch c obital d z2 , dx2 y2 c kh nng xen ph vi cc obital ca 6 phi t phn b dc theo cc trc x, y, z to thnh 4 MO d v * d 2 MO lin kt

d v d
z2 z2

x2 y 2

d* v d * 2 MO phn lin kt

x2 y 2

Cc AO d (dxy, dxz, dyz) c mt e phn b gia cc phi t khng th xen ph c vi cc phi t v chuyn thnh cc MO khng lin 0 kt 1 tm d : 0 ,0 ,0 v nh v cht to d d d phc.
xy xz yz

z y

+ -

d x 2 -y 2
z

d z2

Tm li: 9 AO cht to phc 6 AO phi t t hp 15 MO ca phc cht

s < p

p
dz

= <

< *

<

dx2-y2

<

dz2 < * p
y

dxy = dxz
0 0

dyz
0

= <* dx2-y2

* 2

* p = x

pz

Thng s tch : l hiu s nng lng gia 0

MO

*d v d

S phn b electron trn 2 MO ny ph thuc vo

nh: S phn b cc electron tun theo quy tc Hund ( e phn b ng thi trn 2 MO *d 0d )

*d

0 d

ln: u tin lm y

trc ri mi n

*d

*d

0 d

 So snh vi thuyt TT

S tch mc nng lng ca cc obitan d thnh 2 mc d ,d trong thut trng tinh th ph hp vi s to *d 0d c mc nng lng khc nhau. thnh cc obitan
dz
2

dx2-y2

*z 2

*x2 y2

dxy dxz dyz

Thuyt TT

xy

xz yz

Thuyt MO

Xt 2 phc [CoF6]3- c nh = 156kJ/mol [Co(NH3)6] 3+ c ln = 265kJ/mol Tng s e ha tr ca 2 phc nh nhau l 18e

p* s*

np
ns
* d

(n-1)d

nh
d

p
Co3+

[CoF6]3-

F-

p* s*

np
ns

d
ln

(n-1)d Co3+ [Co(NH3)6]3+

p s

NH3

Cu hnh electron ca 2 phc:

[CoF6]3[Co(NH3)6 ]3+

s s
2

p p
6

00

4
d

*
d

0 6 d

S phn b electron trn 6 MO, Ca 2 phc cht l nh nhau

s p *d ,

s phn b electron trn 2 MO phc khc nhau

0 d

ca 2

[CoF6]3- c 4 e c thn=> c tnh thun t [Co(NH3)6]3+ khng c e c thn => nghch t

 So snh vi thuyt TT

Tng t thuyt TT,theo thuyt MO, [CoF6]3- cng l phc spin cao, c tnh thun t
[Co(NH3)6]3+ cng l phc spin thp,nghch t

Phc bt din c lin kt pi b sung: iu kin to lin kt pi b sung:

Cht to phc c cc AO d

(dxy,dyz,dxz)

Phi t c cc AO p,d, cc MO lin kt v phn lin kt 2 tm ca phi t

C 2 loi tng tc (lin kt ) pi

+ tng tc pi cho nhn (L->M) Khi c s xen ph ca AO d ca cht to phc vi AO p, cha y e ca phi t.Mt phn mt e ca phi t chuyn v pha cht to phc Thng s tch gim xung so vi trong phc cht ch c lin kt

+Tng tc pi cho nhn ngc (M-> L) c hnh thnh do s xen ph gia obitan d cha cp e ca cht to phc v obt *,p* trng ca phi t Mt phn mt e ca cht to phc s chuyn v phi t. Thng s tch delta s tng ln so vi phc khng c lin kt

VD :phc cht [CoF6]3Lin kt c hnh thnh do s xen ph ca obitan 3d ca CO3+ vi obitan 2p c cp e ca F(lin kt cho nhn) *d *d E

s to lin kt lm gim xung, do F- ng u dy ph

lk

Gin nng lng cc MO d ca [CoF6]3-

VD :phc [Cr(CO)6]

c hnh thnh do xen ph gia obitan 0d Lin kt

Cha cp electron ca Cr vi MO * t do ca CO

a)
b) + M M + + + C O + + + C O M C O + M C

O
-

a)s hnh thnh lin kt

b) S hnh thnh lin kt

*d

*d

lk
d

Gin nng lng cc MO d vi phi t CO S to lin kt cui dy ph

ca phc cht

lm

tng ln,do CO ng

Thuyt MO gii thch c t tnh,mu sc ca phc,c dy quang ph

Phi t c th l cht cho

,cho ,nhn

Phi t nhn ,
Dy quang ph:

ln.
b.

Phi t l cht cho ,

I-< Br- < Cl - < SCN- < F-<OH -< H2O< NCS- < NH3 < NO2+<CNCho ,
Nhn yu

Cho

Nhn