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Chimica Inorganica 3

General Electronic Considerations of Metal-Ligand Complexes

Metal complexes are Lewis acid-base adducts formed between metal ions (the acid) and ligands (the base).


The interaction of the frontier atomic (for single atom ligands) or molecular (for many atom ligands) orbitals of the ligand and metal lead to bond formation,


More quantitatively, the interaction energy of stabilization and destabilization, εσ and εσ*, respectively, is defined on the following energy level diagram,


Treating this problem within the LCAO framework comprising metal and ligand orbitals yields,

! = cM"M+ c

L"L

and solving for the Hamiltonian,

H ! = E!

H - E ! = H - E cM!M+ c

L!L

= 0


Left-multiplying by φM and φL yields the set of linear homogeneous equations,

cM !M H ! E !M + cL !M H ! E !L = 0

cM !L H ! E !M + cL !L H ! E !L = 0

which furnishes the secular determinant,

H MM ! E H ML ! ESMLH ML ! ESML H LL ! E

=EM ! E H ML ! ESML

H ML ! ESML EL ! E= 0

E 2 1! SML2( )+ E 2H MLSML !H MM !H LL( )+H MMH LL !H ML

2 = 0


Hypothesis n. 1

H ML = 0E1 =H MM ;E2 =H LL

cM1 =1;cL1 = 0cM 2 = 0;cL2 =1

Hypothesis n. 2

i) H MM =H LL

ii) H MM !H LL

SML = 0

SML ! 0


E 2 1! S2( )+ 2E !S ! "( )+ ! 2 ! " 2 = 0

E =! "S ! !( )± !S ! "( )2 ! ! 2 ! " 2( ) 1! S2( )

1! S2( ) =

! !S ! "( )± !S( )2 + ! 2 ! 2"S! ! ! 2 + " 2 + !S( )2 ! !S( )21+ S( ) 1! S( ) =

E2 =! !S ! "( )+ !2!S" + ! 2 + "S( )2

1+ S( ) 1! S( ) =! !S ! "( )+ !S ! "( )

1+ S( ) 1! S( ) =! 1+ S( )! ! 1+ S( )1+ S( ) 1! S( ) = ! ! "

1! S( )

E1 =! !S ! "( )! !2!S" + ! 2 + "S( )2

1+ S( ) 1! S( ) =! !S ! "( )! !S ! "( )

1+ S( ) 1! S( ) =! 1! S( )+ ! 1! S( )1+ S( ) 1! S( ) = ! + "

1+ S( )

"

#

$$

%

$$

i) H MM =H LL = !; H ML = !;SML = S

Keep in mind that β < 0 and S > 0


E2 =! ! "1! S( ) ; cA2 = !cB2 =

12 1! S( )

E1 =! + "1+ S( ) ; cA1 = cB1 =

12 1+ S( )

"

#$$

%$$


ε

E1 =! + "1+S( )

E2 =! ! "1!S( )

ϕ1 ϕ2

ψ1

ψ2

cM1 = cL1 =1

2 1+ S( )

cM 2 = !cL2 =1

2 1! S( )


ϕM

ϕL

ψ1

ψ2

D = EM ! EL

!D2

D2

EM ! E H ML ! ESMLH ML ! ESML EL ! E

= 0

!D2

! E !B

!B D2

! E= 0

!D2

! E"#$

%&'

D2

! E"#$

%&' =B

2

D 2

4+B 2 = E2

ii) HMM

!HLL

HML

!ESML

= !B


ϕM

ϕL

ψ1

ψ2

D = EM ! EL

!D2

D2

D 2

4+B 2 = E2

if D = 0E+ = BE! = !B

if B <<D

E± =± B 2 +D

2

4= ±D

21+ 4B

2

D 2 !

±D21+ 2B

2

D 2

"#$

%&'= ± D

2+B

2

D"#$

%&'

(

)**

+**

E! = !D2

!B2

D= E

M!

HML

!EMSML( )2

"EML

E+ = +D2

+B2

D= E

L+

HML

!ELSML( )2

"EML

!B2

D

B 2

D

HML

!ESML

= !B

E-

E+


f x( ) = xn

n!dn fdxn

!

"#$

%&n=0

'

(x=0

f x( ) = 1+ x2 )1+ x1!* 121+ x2( )+ 12 2x,

-./01x=0

+ x2

2!1+ x2( )+ 12 + 2x 1+ x

2( )+ 32 2x2

,

-

.

.

.

/

0

111x=0

+ ...

x2 = 4B2

D 2

f x( ) )1+ x2

2!=1+ 4B

2

2D 2 =1+ 2B 2

D 2

E± =± B 2 +D

2

4= ±D

21+ 4B

2

D 2 )

±D21+ 2B

2

D 2

!

"#$

%&= ± D

2+B

2

D!

"#$

%&

2

344

544

Maclaurin Expansion

02/1698 – 14/06/1746


E! = EMH MM

!H

ML!E

MSML( )2

"EML

E+ = ELH LL

+H

ML!E

LSML( )2

"EML

The Wolfsberg-Hemholz approximation provides a value for HML, defined as

H ML = EM + EL( )SML

!"* =EMSML + ELSML ! EMSML( )2

"EML

=ELSML( )2"EML

!" =EMSML + ELSML ! ELSML( )2

"EML

=EMSML( )2"EML

HML

= 1.75EM+E

L( )2

SML

E-

E+


The derivation highlights the following general rules for the construction of MO diagrams, (1) M—L atomic orbital mixing is proportional to the overlap of the metal and ligand

orbital, i.e., SML

corollary A: only orbitals of correct symmetry can mix and ∴ give a nonzero interaction energy (i.e. SML ≠ 0) corollary B: σ interactions typically give rise to larger interaction energies than those resulting from π interactions and π interactions are greater than δ interactions owing to more directional bonding along the series SML (σ) > SML (π) > SML (δ) (2) M–L atomic orbital mixing is inversely proportional to energy difference of mixing orbitals (i.e. ΔEML).


Another issue of interest for the construction of MOs is, (3) The order of the EL and EM energy levels almost always is: σ(L) < π(L) < nd < (n+1)s < (n+1)p   π*L depending on the nature of the ligand   This energy ordering comes directly from Valence Orbital Ionization Energies (VOIE) of metal and main group atoms and PES spectra of molecular ligands.

Atom: 3dn–14s → 3dn–24s 3dn–14s → 3dn–1 3dn–14p → 3dn–1

3d 4s 4p Sc 4.7 5.7 3.2 Ti 5.6 6.1 3.3 V 6.3 6.3 3.5 Cr 7.2 6.6 3.5 Mn 7.9 6.8 3.6 Fe 8.7 7.1 3.7 Co 9.4 7.3 3.8 Ni 10.0 7.6 3.8 Cu 10.7 7.7 4.0

VOIE’s of metal atoms


VOIE’s of ligand atomic orbitals and PES spectra of selected ligands: Atom 1s 2s 2p 3s 3p 4s 4p H 13.6 C 19.4 10.6 N 25.6 13.2 O 32.3 15.8 F 40.2 18.6 Si 14.9 7.7 P 18.8 10.1 S 20.7 11.6 Br 24.1 12.5


PES energies of ligands are in eVs (note: a VOIE is simply the opposite of the ionization energy)


General observations: (1) The s orbitals are generally too low in energy to participate in bonding (ΔEML(σ) is very large) (2) Filled p orbitals are the frontier orbitals, and they have VOIEs that place them below the metal orbitals (3) For molecular ligands, since the frontier orbitals comprise s and p orbitals, here too filled ligand orbitals have energies that are stabilized relative to the metal orbitals

chimica inorganica 3 - chimica.unipd.it. 2018... · chimica inorganica 3 more quantitatively, the...

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