Ly Thuyet Ve Phuc Chat

8/12/2019 Ly Thuyet Ve Phuc Chat

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nh ngh a phc chtPhc chat la hp chat nutmang tinh the co cha cac ion phc tap tch ien tch dng hayam hay phan t trung hoa (phan

t phc) co kha nang ton tai lap trong dung dch


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Cau tao phc chatPhc chat co : cau noi va cau ngoaiCau noi co: chat tao phc va phoi tCo phc chat khong co cau ngoai

V du 1: Na3[Fe(CN)6] co:*Cau noi : [Fe(CN)6]3-*Cau ngoai: Na+

[Fe(CN)6]3- gom co:*Chat tao phc: Fe3+*Phoi t: CN-


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Cau tao phc chatV du 2: [Cu(NH3)4](OH)2 co:

* Cau noi : [Cu(NH3)4]2+* Cau ngoai : OH-

[Cu(NH3)4]2+

gom co:* Chat tao phc: Cu2+* Phoi t: NH3

V du 3: Fe(CO)5 khong co cau ngoaiFe(CO)5 gom co:

* Chat tao phc: Fe* Phoi t: CO


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Thuyet lien ket hoa trPhc chat c hnh thanh nh lienket cong hoa tr cho - nhan gia chatao phc va phoi t+ S phan bo co tnh oi xng cao ccac phoi t xung quanh chat tao ph

do trang thai lai hoa cua cac orbitalhoa tr cua chat tao phc.


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Thuyet lien ket hoa tr

Ph c hexafloridocobaltat(III)Cu hnh : bat dien

Tnh cht t : Thun t

Mu sc ion ph c: xanh l


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Thuyet lien ket hoa trPh c hexafloridocobaltat(III)

Giai thch theo thuyet lien ket hoa tr:


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Thuyet lien ket hoa trPh c hexaammincobalt(III)

Cu hnh: bat dienTnh cht t : Nghch t Mu sc ion ph c: mau vang


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Thuyet lien ket hoa trPh c hexaammincobalt(III)



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Thuyet lien ket hoa trPh c tetracarbonylnikel(0)

Cu hnh: T dinTnh cht t : Nghch t Mau sac: khong mau


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Thuyet lien ket hoa trPh c tetracarbonylnikel(0)



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Thuyet lien ket hoa trPh c tetracloridonikelat(II)

Cu hnh: T dinTnh cht t : Thun t Mau sac: Khong mau


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Thuyet lien ket hoa trPh c tetracloridonikelat(II)



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Thuyet lien ket hoa trPh c tetracloridoplatinat(II)

Cu hnh: Hnh vuongTnh cht t : Nghch t Mau sac: o sam


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Thuyet lien ket hoa trPh c tetracloridoplatinat(II)



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Thuyet lien ket hoa tr

anh gia: Thuyet lien ket hoa tr giai thch

- So phoi tr cua phc- Cau hnh khong gian cua phc

- Tnh chat t cua phc


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Mot so cau hoi khong the giai ap bathuyet lien ket hoa tr

V sao cac tren phc co mau, rieng phctetracarbonylnikel(0) khong co mau?V sao cung la phc bat dien cua cobalt(III) ma v

fluoride th khong co s cap oi electron trong ionCo3+, con vi ammoniac th s cap oi electron lai xayra?Cung hoi tng t oi voi nikel: v sao vi phoi t C

th co s cap oi electron trong nguyen t nikel con vphoi 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, conphc tetracloridoplatinat(II) co cau hnh hnh vuong?


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Thuyet trng tinh the

Noi dung thuyet trng tinh thePhc chat c tao thanh nh tngtac tnh ien gia chat tao phc vaphoi t

Tng tc tnh in gia cht to phc phi tco the lam thay oi cau trucelectron hoa tr cua chat tao phc.


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Khao sat phc bat dientheo thuyet trng tinh the

Phc phc bat dien [CoF6]3- , thuan t,mau xanh l


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Ion Co3+ co cau hnh 3d64s04d05 orbital 3d cua Co3+ gom:

2 orbital 3dx2-y2

va 3dz2

co mat o electronphan bo theo truc toa o



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3 orbital 3dxy, 3dyz va3dxz co mat o electronphan bo gia cac truc toa o


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Do o cac orbitan 3dx2-y2 va 3dz2tng tc vicac ion F- manh hn cacorbitan 3d xy, 3dyz va3dxz. Ket qua 5orbitan 3d tach thanh hai mc nanglng d(eg) (cha cac orbitan va ) vad (t2g) (cha cac orbitan 3dxy, 3dyzva3dxz) theo gian o sau:


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B = Ed - Ed la thong so tach trng tinhthe phc bat dien

Phc [CoF6]3- co B = 1,61 eV.Khi co anh sang chieu qua, electron happhu nang lng 1,61eV va nhay t mcd(t2g) len mc d(eg). Nang lng nay ngvi bc song mau o, v vay phchexafluoridocobaltat(III) co mau xanh da

tri.


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Mau sac cua phc - Day hoa quang pBang 1

Bc song bhap thu(nm)

Nang lng(kJ/mol)

Mau cua anhsang b happhu

Mau cua vatchat

400 435 299 274 Tm Luc vang435 480 274 249 Xanh tm Vang480 490 249 244 Lam Da cam490 500 244 238 Xanh l o

500 560 238 214 Luc Canh sen560 - 580 214 - 206 Lc Vang Tm560 595 206 200 Vang Xanh tm595 605 200 198 Da cam Lam605 750 198 149 o Xanh l


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Mau sac cua phc -Day hoa quang p

Nh bang 1 t mau sac cua phc suy ratr .T ay rut ra day hoa quang pho cua caphoi t cua cung mot loai phc xep thegiam dan gia tr :

CO; CN- > NO2- > NH3 > NCS- > H2O > OH- >> F- > SCN- > Cl- > Br- >I-


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Phc spin thap, phc spin cao

ieu kien cap oi electronViec ghep oi electron trong motorbital tieu ton nang lng (P)Trong phc bat dien, neu so electron>3 va P th phc la phc spin thapNeu < P th phc la phc spin cao


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Phc spin thap, phc spin caoTnh nang lng on nh trng tinh the va trangthai t cua hai phc CoF63- va Co(NH3)63+. Biet

(kJ/mol) cuaCoF63- = 155 va Co(NH3)63+ = 273,2 va P(kJ/mol) =

250,5Giai: 1) Xet trang thai t tnh:

Cau hnh electron hoa tr cua Co3+ la 3d6,* CoF63- co < P nen cau hnh Co3+ la d4d 2

Phc spin cao, thuan t


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Co(NH3)63+ co > P nen cau hnh Co3+ la d6

Phc spin thap, nghch t.


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2) Tnh nang lng on nh trng tinh thePhc spin cao CoF63-:E = 4 (-2/5 ) + 2 3/5 = 2/5 =2/5 155 = -62kJ/mol

Phc spin thap Co(NH3)63+:E = 6 (-2/5 ) + 2 P = -12/5 +2P = -154,68kJ/mol

Ket luan: Phc spin thap ben hn phc spin cao


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Khao sat phc t dien

theo thuyet trng tinh thephc t dien [Cu(NH3)4]2+, thuan t, mau xanh bien.

Khao sat phc t dien


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Khao sat phc t dientheo thuyet trng tinh the

V tr cua cac phan t NH3 so vi ion Cu2+ trenhnh cho thay cac phan t ammoniac tacdung len cac orbital 3dxy, 3dyz va3dxz (d)manh hn tac dung len cac orbitaldx2- y2 vadz2 (d)


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Kh h di


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Ket qua phan lp 3d tach thanh 2: d conang lng cao hn va d co nang lngthap

Kh t h t di


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Phc tetraammin ong(II) coT = 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, phc tetraammin ong(II) co mau xanh ncbien (blue).

Lu y: V oi vi hai phc co cung chat tao pva cung loai phoi tT 4/9 B nen phc t dienkhong co phc spin thap.


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anh gia thuyet trng tinh theu iem

Giai thch c s phong phu va mau sac cua phkim loai chuyen tiepTm ra day hoa quang pho

Giai thch c nguyen nhan gay ra t tnh cua ph(phc spin thap, cao)

Nhc iem- Giai thch khong thoa ang o ben cua cac phthanh chu yeu nh lien ket cong hoa tr.Khong giai thch c ban chat day hoa quang pho

bi


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Thuyetorbitan phan t cho phc chaNoi dung thuyet MO trong phc chat:

Phan t la mot the thong nhat gom cac hat nhanguyen t va mot lp vo electron phan t.Electron trong phan t co mot trang thai rieng mo ta bang ham song goi la orbitan phan t.Xay dng lp vo electron phan t theo phng phahp tuyen tnh cac orbitan nguyen t (LCAO)Cac AO to hp c vi nhau khi co cung tnh o

va co nang lng gan nhau.Phc chat c tao thanh co s giam o suy biecac phan lp cha nhieu orbitan.


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Phng phap thiet lap s o nang lng lvo electron cua phan t bang cach to hp

tuyen tnh cac ocbitan nguyen t(LCAO Linear Combination of Atomic Orbitals)a) Tha nhan rangchco cac ocbitan nguyen

t (AO)hoa trla b bien oi ro ret khi tathanh phan t do o ch to hp cac AOtr vi nhau, cac AOcon laichuyen vao

phan t di dang cac ocbitan phan tkhong lien ket(ngha la cac ocbitan naykhong anh hng en o ben cua phanv gi nguyen nang lng co trong nguye


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b) Ch cac AO cua cac nguyen t cotnh oixnggiong nhau mi to hp vi nhau.

c) S to hp cua cac AO cua cac nguyen cang manh khi chungco nang lng canggannhau va chung xen phu nhau cang l.

d) Ket qua to hp tuan theo quy tac: aAOcua nguyen t A to hp vi bAO cuanguyen t B se tao thanhaMOlk , aMOplk

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

Phng phap LCAO


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Phng phap LCAO

Khao sat phc bat dien phoi t khong


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Khao sat phc bat dien phoi t khongorbital tao lien ket theo thuyet MO

Xet phc CoF63-

S phan bo cua cac ion F- so vi ionCo3+cho trenhnh

Kh h b di h i kh


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Khao sat phc bat dien phoi t khongorbital tao lien ket theo thuyet MO

S to hp theo LCAO:

6 AO 4s , 4px , 4py , 4pz, va cua Co3+ to hpvi 6 AO 2px cua 6 ion F-.Ket qua tao thanh 12 MO gom:6 MO lien ket va 6 MOphan lien ket

h h b d h kh


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Khao sat phc bat dien phoi t khoco orbital tao lien kettheo thuyet MO

V du ve s to hpS to hp gia 4s cua Co3+ va 6 AO 2px cua 6 ion

F-

Kh h b di h i kh


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V du ve s to hpS to hp gia px cua Co3+ va 2 AO 2px

cua 2 ion F-

phan bo tren truc x



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V du ve s to hpS to hp gia 4dx2-y2 cua Co3+ va 4 AO 2px cua

4 ion F-

phan bo tren truc x va truc y


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Khao sat phc bat dien phoi t kho

co orbital tao lien kettheo thuyet MONgoai ra Co3+ con 3 orbitan 3dxy, 3dyz

va 3dzx khong to hp chuyen vao tronphan t thanh MOkhong lien ket.

Phng phap to hp LCAO cho gian o nanglng cac phc spin cao CoF63- va phc spin thapCo(NH3)63+o khong co lien ket trang sau :


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Nhan xet ve phc da tren gian o cau

electron hoa tr phan tCo(NH3)63+ la phc spin thap ( ms = 0), nghch tCoF63- la phc spin cao ( ms = +2), thuan t.Nang lng tach trng tinh the = E*d - E 0dCac phc nay co the co mau do0d chaelectron 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 caoCoF63- do co lien ketd ben hn va tren*dkhong co electron.

Phc bat dien phoi t co orbital tao lien


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ptheo phng phap MO

S xuat hien cac MOlam thay oi thong sotach.Trng hp phoi t nhan( -acceptorligand):

Cac orbital co the tao lien ketcua phoi tto hp vi cac orbital dcua chat tao phclam tang , lien ket0 chuyen thanhlk chaelectron, ket qua lam phc ben vng hn.


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T cac gian o phc bat dien rut ra cac nhan xet 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 MOlien ket co nang lng cang tha

3)Trong trng hp phoi t la chat chophc cang benkhi cang nho v MOlien ket co nang lng cangthap.

4)o ln tang dan theo tnh chat phoi t. Quy luat na

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


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Nhan xet rut ra t cac gian o phc bat die


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Nhan xet rut ra t cac gian o phc bat die


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Nhan xet rut ra t cac gian o phc bat


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Nhan xet rut ra t cac gian o phc bat

Nhan xet 4:o ln tang dan theo tnh chat phoi t. Quy lua

nay giai thch c ban chat cua day hoa quang p

Phoi t nhan> phoi t khong tao lien ket< phoi tcho


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