spektra senyawa kompleks logam transisi 2

8/19/2019 Spektra Senyawa Kompleks Logam Transisi 2

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S P E K T R A

E L E K T R O N

I K

S E

N Y A W

A K O M P

L E K S

S e n y a w

a L o g

a m T r a n s i s

i

03/14/161Departemen Kimia Fakultas Matematika dan lmu !engeta"uan #lam $ni%ersitas

ndonesia

Dr. rer. Nat. Agustino Zulys M.Sc.



Langkah penentuan Ground Term

p2

ML & MS

Microstate

Table

States (S, P, D)

Spin multiplicity

Terms3

P,1

D,1

S

Ground state term3 P



Untuk senyawa kompleks logam transisi

empertim!angkan d 1"d 1#

d 2

3 $ , 3 P, 1G, 1 D, 1S

Untuk 3 atau le!ih elektron adalah proses yang sangat pan%ang

&um Gl'(k is s(hon ta!uliert orher*



Transitions antara term electron memberikan spektra elektronik



3P

3F

∆ E

∆ E = 15 B

B adalah ara!eter "acah dan engu#uran tola#an antar ele#tron

dala! ion

$eadaan% yang

!e!ili#i sin

!ultilicity yang

sa!a

$e#uatan relati& intera#si #oling'

MS = Σ !s (ML = Σ !l ( ML ) MS

*ang !ana #eadaan dasar+



Aa#ah #eadan dasar ter! untu# #on&igurasi % dan d%+

d,' %D -P -F %P %D %F % %/

$eadaan dasar -P -F #arena !e!ili#i sin !ultilicity ter0esar

d5' %D -P -F %P %D %F % %/ %S %D %F % % -D - 2S



$eadaan dasar ion 0e0as dn

d- )% )1 1 %

5D

d5 )% )1 1 %

2S

M4 = )%% 4 = % D ter!

MS = -6% %S71 = 5

M4 = 4 = S ter!

MS = 56% %S71 = 2

d2 )% )1 1 %

5DM4 = )%.% 4 = % D ter!

MS = % %S71 = 5

d3 )% )1 1 %

-FM4 = )33 4 = 3 F ter!MS = 36% %S71 = -



d,

)% )1 1 %-F

d8 )% )1 1 %3F

d9 )% )1 1 %

%D

M4 = )3.3 4 = 3 F ter!

MS = 36% %S71 = -

M4 = )3.3 4 = 3 F ter!

MS = %6% %S71 = 3

M4 = )%% 4 = % D ter!

MS = 16% %S71 = %

$eadaan dasar ion 0e0as dn



d)d transitions in high sin co!le:es

round State

d1 d9 %D

d% d8 3F 3P

d3 d, -F -P

d- d2 5D

d5 2S

$eadaan dasar ion 0e0as dn untu# se!ua #on&igurasi



2Eg

2T2g

E&e# !edan #ristal ada ter! ion 0e0as untu# #o!le#s d1

2T2

2E

6 Dq

4 Dq

2D

tetrahedral &ield &ree ion octahedral &ield

d1

d2



2Eg

2T2g

2D

Energy

ligand &ield strength; ∆oct

<ntu# ion d2 ada !edan o#taheral !enghasil#an siliting yangsa!a dengan d1; tetai

!ultilicity nya 5; yaitu 5Egand 5T2g

Diagram tingkat energi diagramuntuk ion d1 pada medan &" 'eld



6 Dq

4 Dq2Eg

2T2g

2D

Energy

ligand &ield strength; ∆oct

$o!le#s d9 !e!ili#i ting#at energi yang sa!a dengan #o!le#s d1; tetai

urutannya #e0ali#an

d- d9

Diagram tingkat energi diagramuntuk ion d1 pada medan &" 'eld



A

ν / cm-1)

3 % 1

d1 oct >?i@/%237

E

4F strength

Diagra! rgel untu# d1, d-, d2, d9

0 ∆∆

D

d-, d9 tetrahedral

T2g or T2

T2g or T2

d-, d9 octahedral

Eg or E

d1, d2 tetrahedral

Egor E

d1, d2 octahedral

%Eg %?%g

2Eg

2T2g

2

D



S

d1 d9 %D

d% d8 3F 3P

d3 d, -F -P

d- d2 5D

d5 2S

D

T2(g) and E(g)

&ree ion ligand &ield

S

d1 d9 %D

d% d8 3F 3P

d3 d, -F -P

d- d2 5D

d5 2S

P

F

&ree ion ligand &ield

?

()e*t medan ligand padakeadaan dasar



ctahedral d% co!le:

3P' high reulsion

n a 4F; these or0itals are una&&ected

:%)y% 7 %

:%)y% 7 y

:%

)y%

7 ::y 7 %

:y 7 :

:y 7 y

: 7 y

3F' lo reulsion

n a 4F; or0itals in the t%g set go don in energy; or0itals in the eg set go u in energy

: 7 %

y 7 %

:y 7 :%)y%

3

?1g

3 A%g

3?%g

3?1g

eg eg singly degenerate; high energy

eg t%g trily degenerate; !ediu! energy

t%g t%g trily degenerate; lo energy

d% d,



ctahedral d3 co!le:

-P' high reulsion

n a 4F; these or0itals are una&&ected -?1g

-F' lo reulsion

?he order o& energy leels is the oosite to that &or a d% ion

-?1g

-?%g

- A%g

d3 d8@sa!e ter!s; di&&erent sin

rgel diagra! &or d% d3 d, d8 ions


http://slidepdf.com/reader/full/spektra-senyawa-kompleks-logam-transisi-2 19/634igand &ield strength @DG

Energy

rgel diagra! &or d ; d ; d ; d ions

Huantu! Mi:ing

d%; d, tetrahedral d%; d, octahedral

d3; d8 octahedral d3; d8 tetrahedral

F

P?1 or ?1g

?1 or ?1g

A% or A%g

?1 or ?1g

?% or ?%g

A% or A%g

?% or ?%g

?1 or ?1g



Calculating BI and : d, octahedral co!le:

4A2g

4T1g

4T1g

4T2g

10 Dq

6 Dq

2 Dq

x

x

15 B'

A

>Co@/%2%7

ν1

ν2

ν3

%5 % 15 1

ν12

ν3

ν

1

= 8 c!)1

ν2 = 12 c!)1

ν3 = 19 - c!)1

6 c!)1

rgel diagra! &or d% d3 d, d8 ions



F

P

4igand &ield strength @DG

Energy

rgel diagra! &or d ; d ; d ; d ions

d%; d, tetrahedral d%; d, octahedral

d3; d8 octahedral d3; d8 tetrahedral

A% or A%g

?1 or ?1g

?% or ?%g

A% or A%g

?% or ?%g

?1 or ?1g

?1 or ?1g

?1 or ?1g



P

F

15 B'15 B

x

x

10 Dq

6 Dq

2 Dq

T1(g)

T1(g)

A2(g)

T2(g)

Energy leel diagra! &or oct d%; d,; tet d3; d8ν1' : 7 8 DG

ν2' % : 7 2 DG 7 15 BI

ν3' : 7 18 DG

ν1

ν2

ν3

ν1' ?%@g ?1@g

ν2' ?1@g@P ?1@g

ν

3' A%@g ?1@g



P

F

x

x

15 B'15 B

15 B > 15 B'

Energy diagra! &or oct d3; d8; tet d%; d,

10 Dq

2 Dq

6 Dq

A2(g)

T1(g)

T2(g)

T1(g)

∆ = 10 Dq



Calculating BI and : d, tetrahedral co!le:

A

%5 %

>CoCl-%)

15 1 5

ν12

ν3

6 c!)1

4A2

4T1

4T2

4T1

10 Dq

2 Dq

6 Dq

x

x

15 B'

ν1 = 3 3 c!)1 " region

ν2 = 5 8 c!)1 isi0le

ν3 = 15 c!)1 isi0le



?he Nehelau:etic E&&ect

) so!e coalency in M)4 0onds J M and 4 share electrons

) e&&ectie sie o& !etal or0itals increases

) electron)electron reulsion decreases

Nehelau:etic series o& ligands

F) K /% K N/3 K en K >o:alate2- K >NCS- K Cl- K Br - K -

Nehelau:etic series o& !etal ions

Mn@ K Ni@ Co@ K Mo@ ( "e @L K Fe@ K r@ K Co@ K Mn@L

cloud e:anding



1

%

3

-

5

rgel Diagra!; d5 oct and tet

4igand Field Strength; DG @c!)1

5 1

Energy @c!)1

-E@g

-?%@g

-E@g; - A1@g

-?%@g

-?1@g

2 A1@g

-?%@g

-?1@g

- A%@g

-?1@g

2S

--P

-D

-F



d5 octahedral co!le:

ε

>Mn@/%2%7

6 c!)1

% %5 3

Multile a0sortion 0ands

Lery ea# intensity

-?%g @D

-Eg @D-?1g@

-Eg @

- A1g @

-?%g @

.1

.%

.3

?ransitions are &or0idden



Sin Selection "ule

∆S =

?here !ust 0e no change in sin !ultilicity during an electronic transition

4aorte Selection "ule

∆ l = 1

?here !ust 0e a change in arity during an electronic transition

Selection rules deter!ine the intensity o& electronic transitions

g

u



ε

ν / cm-1)

2Eg

2T2g

2D

E

∆oct

>?i@/%237; d1; h &ield

1 % 3

.1

.%

.3

Sin alloed

4aorte &or0idden

?ransition 0eteen d or0itals



>L@/%237; d% h

Sin alloed 4aorte &or0idden

F

P

DG

A%g

?%g

?1g

?1

?%

A%

?1 ?1g

d, tetrahedral d% octahedral

ε

1 3 ν / c!)1−

1

%

5

-?1g

-?%g

-?1g

- A%g

%5 % 15 1 5 6 c!)1

>CoCl-%); d, ?d

3?1

3?%

3 A%

3?1

ε

2

-

%



Aturan Sele#sintensitas arna suatu #o!le#s tergantung dari..

1. 4aorte Selection "ule

%. Sin Selection "ule

?ransisi yang !engi#uti aturan sele#si

?ransisi diiin#an @alloed

transition diso0eys selection rules

?ransisi terlarang @&or0idden

ntensitas arna



Aturan Sele#si 4aorte

/arus ada eru0ahan notasi aritas

s)or0ital

gerade

d)or0ital

gerade

)or0ital

ungerade

e.g. )or0ital #e d)or0ital diiin#an !enurut aturan sele#si 4aorte

d)or0ital #e d)or0ital terlarang !enurut aturan sele#si 4aorte



$o!le#s #tahedral

Centrosy!!etric' or0ital)or0ital t%g dan eg

?ransisi d)d terlarang !enurut aturan sele#si 4aorte

?etrahedral co!le:es

non)Centrosy!!etric' or0ital t% dan e

aturan sele#si 4aorte tida# terali#asi

?ransisi antar or0ital)d @g terlarang !enurut aturan sele#si 4aorte

$o!le# tetrahedral 0iasanya !e!ili#i arna yang le0ih #uat dari ada #o!le#

analog o#tahedral



alloed&or0idden

Aturan Sele#si Sin

?ida# 0oleh ada eru0ahan Sin

S = 0



inersion

centre

"ela:ation o& the 4aorte Selection "ule &or ?etrahedral Co!le:es

ctahedral co!le:

Centrosy!!etric

4aorte rule alies

?etrahedral co!le:

Non)centrosy!!etric

4aorte rule rela:ed

r0ital !i:ing'h co!le: d eg and t%g t1u

?d co!le: d e and t% t%

n tet co!le:es; d )or0itals hae so!e p character

ntenstity o& transitions in d5 co!le:es



ntenstity o& transitions in d co!le:es

2S

1

%

3

-

5

-

-P

-D

-F

DG @c!)1

5 1

Energy @c!)1

-E@g-?%@g-E@g;

- A1@g

-?%@g

-?1@g

2 A1@g

-?%@g

-?1@g

- A%@g

-?1@g

4aorte &or0idden

Sin &or0idden

Oea# transitions occur due to' <nsy!!etrical Li0rations @i0ronic transitions

Sin)or0it Couling



"ela:ation o& Selection "ules

ctahedral co!le:es' centrosy!!etric

4aorte rule rela:ed 0y i0ronic couling

?etrahedral co!le:es' non)centrosy!!etric

4aorte rule rela:ed 0y or0ital !i:ing

Selection "ules

Sin Selection "ule ∆S =

?here !ust 0e no change in sin !ultilicity during an electronic transition

4aorte Selection "ule ∆ l = 1

?here !ust 0e a change in arity during an electronic transition

d5

co!le:es' i0ronic couling and Sin)or0it couling



Broadening -E @



-Eg; - A1g

2S

1

%

3

-

5

-

-P

-D

-F

DG @c!)1

5 1

Energy @c!)1

-?%g

-?%g

-?1g

2 A1g

-?%g

-?1g

- A%g

-?1g

ε

6 c!)1

% %5 3

.1

.%

.3

Broadening

1. Molecular i0ration -?%g @D

-Eg @D-?1g@

-Eg @

- A1g @

-?%g @

-Eg

-Eg

-?%g

-?1g2 A1g

E

DG

>Ni@/ %7 d8



Broadening

%. Sin)r0it Couling

Couling 0eteen an alloed and

&or0idden transition hich are ery

close in energy

MS- MS ( ML - MS ( ML ) MS

A

1- 5 %5

>Ni@/%2% ; d8

1

ν / cm-1)

>Ni@/%2%7; d8

3

F

1D

3

A%g

3?%g

1Eg

3?1g

DG6B

E6B

3?1g 3 A%g

sin &or0idden transition

3 ?h h ? ll ?h A li l l i d t l t i



A

ν / cm-1)3 % 1

>?i@/%237; d1

%?%g

%Eg

%B1g

% A1g

3. ?he ahn)?eller ?heoru!' Any non)linear !olecule in a degenerate electronic

state ill undergo distortion to loer itIs sy!!etry and li&t the degeneracy

d3 - A%g

d5 @high sin 2 A1g

d2 @lo sin 1 A1g

d8 3

A%g

Degenerate electronic ground state' ? or E

Non)degenerate ground state' A

?h S h i l S i



eg

t %g

eg

t %g

ea# &ield ligands

e.g. /%

high sin co!le:es

strong &ield ligands

e.g. CN)

lo sin co!le:es

) K Br ) K S%) K SCN) K Cl)K N3) K F) K /) K o:%)

K /% K NCS) K C/3CN K N/3 K en K 0y

K hen K N%) K hosh K CN) K C

?he Sectroche!ical Series

?he Sin ?ransition

∆ ∆

d5



?ana0e)Sugano diagra!s

E6B

∆6B

%?%g

- A1g;-E

-?%g

-?1g

-?%g

-

?1g

% A1g

-?%g

%?%g

2 A1g

%Eg

- A%g;%?1g

%?1g

% A1g

-Eg All ter!s includedround state assigned to E =

/igher leels dran relatie to S

Energy in ter!s o& B

/igh)sin and lo)sin con&igurations

Critical alue o& ∆

d5

OEA$ FE4D S?"N FE4D

?ana0e Sugano diagra! &or d% ions 1



?ana0e)Sugano diagra! &or d% ions

E6B

∆6B

>L@/%237' ?hree sin alloed transitions

ν1 = 1, 8 c!)1 isi0le

ν

2

= %5 , c!)1 isi0le

ν3 = o0scured 0y C? transition in <L

1

ε

3 ν / c!)1−

1

%

5

%5 , = 1.--

1, 8

∆6B = 3%

ν3 = %.1ν1 = %.1 : 1, 8

∴ ν3 = 3, c!)1

= 3%



ν1 = 1, 8 c!)1

ν2 = %5 , c!)1

ν3 = 3, c!)1

∆o = ν3 J ν1

= 19 % c!)1

3P

3F

x

x

10 Dq

6 Dq

2 Dq

3T1g

3T1g

3A2g

3T2gν1

ν3

∆o 6 B = 3%

B = 2 c!)1



E6B

∆6B = 3%

ν1 = 1, 8 c!)1

ν2 = %5 , c!)1

ν

1

ν2E6B = -3 c!)1

E6B = 3 c!)1

E6B = -3 c!)1 E = %5 , c!)1

B = 2 c!)1

∆o 6 B = 3%

∆o = 19 % c!)1

Calculating ν = 1, - c!)1



Calculating ν3

E6B

∆6B

ν1 = 1, - c!)1

ν2 = %- 5 c!)1

= %-

E6B = 3- c!)1

E6B = %- c!)1

Ohen ν1 = E =1, - c!)1

E6B = %-

so B = ,%5 c!)1

Ohen ν2 = E =%- 5 c!)1

E6B = 3-

so B = ,%5 c!)1

& ∆6B = %-∆ = %- : ,%5 = 1, - c!)1

1, - 1 i i0l



4A2g

4T1g

4T2g

4T1g

10 Dq

2 Dq

6 Dq

x

x

15 B'For h d

3; ∆o = ν1 = 1, - c!)1

∆o 6 B = %-

B = ,%5 c!)1

Energy diagra! &or octahedral d3 co!le: ν1 = 1, - c!)1 isi0le

ν2 = %- 5 c!)1 isi0le

ν3 = o0scured 0y C? transition

d and d1 ion hae no d d transitionsd and d1 ions



?iF- d ion

?iCl- d ion

?iBr - d ion

?i-

d ion

d and d1 ion hae no d)d transitions

>Mn-) Mn@L d ion

>Cr %,) Cr@L d ion

>Cu@MeCN-7 Cu@ d1 ion

>Cu@hen%7 Cu@ d1 ion

Zn%7 d1 ion

e:tre!ely urle

0right orange

d and d ions

hite

hite

orange

dar# 0ron

colourless

dar# orange

hite

Charge ?rans&er ?ransitions

4igand to !etal charge trans&erMetal to ligand charge trans&er



Charge ?rans&er ?ransitions

4igand)to)!etal charge trans&er

4MC? transitions

Metal)to)ligand charge trans&er

M4C? transitions

Md

4π

4σ

4π∗

t%gQ

egQ

d)d transitions

Selection rules



Selection rules

C? transitions are sin alloed and 4aorte alloed

?ransitions occur &ro! a

singlet S to a singlet ES

∆S =

?ransitions occur 0eteen

!etal 0ased or0itals ith d)

character and ligand 0ased

or0itals ith )character

∆l = 1

C? transitions are there&ore !uch !ore intense than d)d transitions

4MC? ?ransitions



4MC? ?ransitions

>Mn-); dar# urle

e- oor !etal @electroositie; high charge

Cr@; d3 ion; Mn@L; d ion

4MC? = ligand to !etal charge trans&er

e- rich ligand

%); Cl); Br

);

)

sin)alloed 4aorte alloed

Mn

-

M diagra! o& Mn-)

4@t1 M@e 1, , c!)1



nd

@n71

π

σ

a1 ;t%

t%

a1

e; t%t1 ;t%

M -4M4-

∆t

4@t1 M@e 1, , c!

4@t1 M@t%Q %9 5 c!)1

4@t% M@e 3 3 c!)1

4@t% M@t%Q -- - c!)1

@n71s

a1

t%

t%

t1

e

t%Q

a1Q

tQ

4MC? ?ransitions sin)alloed 4aorte alloed



4MC? ?ransitions sin alloed 4aorte alloed

l o g @ ε 6 4 ! o l ) 1 c

! ) 1 A

λ / n!2

@1, c!)1

3

-

1

%

%

@5 c!)1

-

@%5 c!)1

4MC?

d)dd)d

denti&ying charge trans&er transitions

ntensity

Solatochro!is! ) ariation in a0sortion aelength ith solent

>CrCl@N/35%7; Cr@; d3

Cr

N/3

N/3/3N

/3N

/3N

%7

Cl

Charge)?rans&er ?ransitions' M4C? sin)alloed 4aorte alloed



Charge ?rans&er ?ransitions' M4C?

>Cu@hen%7; dar# orange

e- rich !etal; lo charge; loer S

Cu@; d1 ion

M4C? = !etal to ligand charge trans&er

π)accetor ligand ith lo)lying πQ or0itals

1;1)henanthroline

ε

λ / n!- 5 2

3

-

5

1

%

λ!a: = -58 n!

sin alloed 4aorte alloed

N

N

N

NCu

Charge)?rans&er ?ransitions' M4C? sin)alloed 4aorte alloed



Charge ?rans&er ?ransitions' M4C?

>"u@0y3%7; 0right orange

e- rich !etal; lo charge; loer S

"u@; d2 ion; lo sin

M4C? = !etal to ligand charge trans&er

π)accetor ligand ith lo)lying πQ or0itals

%;%I)0iyridine

ε

λ / n!3 5

λ!a: = -5% n!

M4C?

sin alloed 4aorte alloed

% -

π)πQ

"u

N

NNN

N

N

%7

R nterelectron reulsion 4i!its o& 4F? J e:istence o& electronic states



R "ussel)Saunders couling Collecting !icrostates into ter!s

<sing /undIs rules S and ES ith sa!e !ultilicity

R E&&ect o& 4F on &ree ion ter!s rgel diagra! &or d1; d-; d2; d9 ions >?i@/%237

R rgel diagra! &or d%; d3; d,; d8 ions >Ni@/%2%7

Calculating ∆; : and BI >Co@/%2%7; >CoCl-%)

"acah ara!eters in &ree ions and co!le:es

?he Nehelau:etic e&&ect

rgel diagra! &or d5 ions >Mn@/%2%7

R Sin and 4aorte Selection "ules Selection rules &or h and ?d co!le:es

4i&ting selection rules

rigin o& 0and 0roadening >Ni@/%2%7

; >Mn@/%2%7

; >?i@/%237

R?ana0e)Sugano diagra!s 4o sin co!le:es >Mn@CN2-)

Calculating E; BI and ∆ >Cr@/%237; >L@/%237

R C? transitions 4MC? >CoCl@N/35%7; >Mn-)

Menghitung ∆oct menggunakan T-S. misal! d"# V(H2O)63+



$%

∆'%

ara! cocokan energi yang teramati ke diagram.

emudian cari nilai splitting parameter# ∆o%# yang

memberikan dua eksitasi dengan ratio "*#+,,%+#,, /

.00

Spekturm teramati

υ1: +#,, cm-

υ"! "*#+,, cm-

1ertama# 2elas υ meru2uk pada 3T 3T"

υ" bisa 3T 3A" atau 3T 3T.

4asio υ"%υ / .00 dihasilkan pada ∆o % / 3

$nergi eksitasi5ntuk υ! $% / +#,, cm- % / "6 menghasilkan

/ 7, cm-

menggunakan 3 / ∆o% / ∆o%7, didapat

∆o / 6#,,, cm-

Menentukan ∆o dari spektra d 3



Lowest energy transition + ∆o

mi8ing

mi8ing

S"#$t%u& #l#$t%oni$ 'i(H ) +2



isi0le in&rared<L

Hijau32g !

3T2g

32g !1Eg

>Ni@/%2%7

S"#$t%u& #l#$t%oni$ 'i(H2)*+

λ,

$o!le: terlihat 0erarna hiau; #arena !enyera sangat le!ah ada 5 n!;

Panang gelo!0ang dari cahaya hiau



turan Seleksi

-menentukan intensitas serapan)

Laporte rule

g → g .or!idden -transition d"d .or!idden)

Tetapi g → u allowed -transition d"p allowed)

Spin rule

Transition antara keadaan multipisiti !er!eda .or!idden

Transition antara keadaan multipisiti yang sama allowed

spektra senyawa kompleks logam transisi 2

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