Course Outline
Academic Year 2017/18
Chapter 8. The bonding in solids. Band Theory: the linear chain of hydrogen
atoms. Bloch functions. Peierls distortion. Bonds in two and three dimensions. The
electronic structures of solids.
Chapter 12. Synthesis of solids. The ceramic method: solid state reactions at high
temperatures. Sol-gel methods. Other synthetic procedures.
Seminar Contents:
- Basic solid state chemistry, A. R. West, 2a Ed. John Wiley and Sons: 2014.
2+ 2+
N N
N Cl Cl N
Co Co
N NH3 H3N N
N N
N-N = H2NCH2CH2NH2
6+
[Co]
H HO
O OH
[Co] Co [Co] = Co(NH3)4
O O
H HO H
[Co]
Remove Cp
Ligands: neutral or charged atoms or molecules that posses one or more donor atoms (i.e. atoms that can
share electron density from a lone pair). General symbol: L
Neutral L do not contribute to the M oxidation state. They behave as 2e- donors. For instance:
:NH3 (2e-); en = H2NCH2CH2NH2 (2x2=4e-). In general L or L L, etc.
Anionic L contribute with 1- (in general n-) to the M oxidation state. In the covalent formalism they are
viewed as radicals and act as 1e- donors. General representation: X
2-
O charge -2; O 2e- donor
etc.
a ligand like
H H
H3C C CH3 H3C C CH3
C C C C
O O O O
Cl Cl
M Cl
M M M M
- - -
1e 3e 5e M
chelating ligands
B
Tp': tridentate
N
N
N
N
N
N
Crown ethers; cryptands,...: multidentate ligands
π
M L
σ
π
F as radical F σ M equiv. to F M
3e-
O O M, but also: O M
2e- 4e-
R O M O 1e-
R
M O 3e- equiv. to M O
R R
M O R 5e-, M O R
lineal
2-
Similar comments for R2N y R N
π
π-ACCEPTOR LIGANDS. They posses empty, low-lying orbitals of π symmetry: M L π back-donation
σ
Some Examples: CO, NO, PR3, C C , C C
Also H2, O2, N2,..........
H2 : σ* m.o.
O2, N2 : also π* m.o.
etc, etc.
Alkyl, aryl and related groups. Formally monoanionic, e.g. CH3-, C6H5-, .... They are viewed as radicals, hence 1e- donors
M M
2e-; η2 2e-; η2
[M]
η4 - C4H6
Ciclopentadienyl (5C)
ARENES
three coordination sites (L3); 6e- donor ligands
(η 6-C6H 6)
Cr
Cr(C6H6)2
CrCl3(NH 3)3 :
3(Cr3+)+6(Cl-)+6(NH3)=15e-
7(Mn)+(CH3)+5 x 2(CO)=18e- 7(Mn)+(CH3)+5 x 2(CO)=18e-
+1 (-1) (+2) (-1) (-1)
Mn(CH3)(CO)5 Ni(C6H5)Cl(PMe3)2
+1 (-1)
Mn(η -C3H5)(CO)4: Mn(I), d7, 6-coordinate.
3
EAN= 7(Mn)+3(al.)+8(4CO)=18e-
O
C H
(η5-C5H5) Rh Rh (η5-C5H5) H C C
H
C
O
4(C)+3(H)+1(C-C)
Planos NODALES = 2
Radial extension of atomic orbitals nd, (n+1)s y (n+1)p
A1g 1 1 1 1 1 1 1 1 1 1 X2 + y2 + z2
A2g 1 1 -1 -1 1 1 -1 1 1 -1
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1
ML6(σ) ML6(σ + π) 6L(π-donors)
eg* eg*
∆0
∆0 t2g
t2g
t2g
t2g
eg* eg*
t2g
∆0
t2g ∆0
t2g
3.- Nature of M 1st T.S. < 2nd T.S. < 3rd T.S.
SPECTROCHEMICAL SERIES
4.- Nature of the ligands
I- < Br- < S2- < SCN- < Cl- < NO3- < N3- < F- < OH- < O2- <... Weak-Field Ligands
...< H2O < NCS- < CH3CN < py < NH3 < en <... Intermediate-Field Ligands
...< CH3 < H- ~ CN- < PR3 < NO < CO Strong-Field Ligands
The 18-e- rule (EAN rule)
n(d) n(VE)
0 12
1 13
t1u* 2 14
3 15
4 16
5 17
a1g* 6 18
np 7 19
8 20
9 21
10 22
ns eg*
(n-1)d ∆0 t
2g
σ
M L
Class I
a1g* 1 17
np 2 18
4 16
5 17
6 18
ns eg* 8 16
(n-1)d ∆0 t
2g
σ
M L
Class II
Cr(CO)6