Coordination compounds

(complex)
complex: used by chemists for compounds that consist of
(several) other compounds that can exist separately

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 Coordination compounds
(complex)
coordin Lewis acid
ation
sphere
(inner) central atom

acceptor
No. of donors
exceeds the
value of donor
oxidation
number ligands

Lewis base
usually (poly-nuclear)
ions + counterions 2
 Some of further basic concepts

Ligands:
monodentate – a single donor atom (H2O, CN-, F- … )
polydentate – their geometry enables to occupy
(bi-, tri- ...) more than a single coordination position
 several donor atoms (chelate agents)
(e.g. ethylendiamin H2N-CH2-CH2-NH2)

Coordination number: number of donor atoms

coordinated in the inner sphere

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 chelate complexes

EDTA
Ethylendiamin
(en) Ethylendiamintetraacetate(4-)

bridging ligands

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Coordination compounds: bonds/structure

Alfred Werner, Swiss, 1866-1919, Nobel Prize 1913

Showed that transition metals create complexes with

square, tertrahedral, octahedral structure

trans-

cis-

geometrical isomers
e.g. cis-[PtCl2(NH3)2] trans-[PtCl2(NH3)2]
diammin-dichloridoplatinum(II) complex
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Typical space structures of complexes

Trojnásobne zastrešená
Trigonálny dodekaéder trigonálna prizma

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Geometrical isomerism for octahedral structures

cis- trans- mer- fac-

Info: Optical isomerism: mirror image – enatiomers

chirality, chiral molecules

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 Coordination compounds: bonds/structure
Valence bond theory with hybrid AO in most cases
enables explanation of the structure

coord. No. form of coord. sphere examples

2 – SP linear [CuCl2]- [Ag(S2O3)2]3-
4 – SP3 [Co(NCS)4]2- [NiCl4]2-
D3S tetrahedron [BF3(NH3)]
4 – DSP2 [Mn(H2O)4]2+ [PdCl4]2-
SP2D square [Pd(NH3)4] 2+ Ni(CN)4]2-
6 – D2SP3 [Fe(H2O)6]2+
SP3D2 octahedron [Fe(CN)6]3- [FeF6]3-
[PdCl6]2-

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 paramagnetic [NiCl4]2- unpaired electrons

Ni(II) -[NiCl4]2–

sp3
High-spin complex

Ni2+

28Ni

3d 4s 4p

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 diamagnetic [Ni(CN)4]2- paired electrons

Ni(II) -[Ni(CN)4]2–
dsp2

valence Ni2+
Ni2+

Ni
3d 4s 4p
Low-spin complex

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Coordination compounds: bonds/structure

??????
metal-ligand bond is weaker than „usual“ covalent b.

Some complexes use inner „d“ orbitals

others use outer „d“ orbitals

Transition metal complexes use to be intensively colored

MO theory

simplified approximations
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 Crystal field theory
Central atom in electrostatic field
of (ionic) ligands (as point charges)
(electrostatic theory of ligand field)
Splitting of „d“ levels: octahedral complex

Ligand
field
Energy

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 Why the transition metal complexes are colored?

octahedral
eg
Energy

t2g

complex is violet d-d transitions

splitting of „d“ levels: tetrahedral complex

t2
Δ
Energy

d
e
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 low and high-spin complexes [Fe(CN)6]3- [FeF6]3-

Energy [Fe(CN)6]3- [FeF6]3-

eg
Δ
Δ

t2g
Fe3+
Fe0
5d 4s

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 Relative ligand field strengths

Low-spin complexes High-spin complexes

Spectrochemical series

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Oxidation-reduction (redox) reactions: change of oxidation state

-IV, -III ... 0, I, II ... VIII electron balance:

oxidation donated e– = accepted e –
reduction x.m = y.n

x BAox1 + y DCox2  x EAox1+m + y FCox2-n

Reducing agent oxidizing agent

(electron donor) (electron acceptor)

Example: Br20 + 5HCl IO + H2O  2 HBrVO3 + 5HCl -I

partial Br02  2BrV + 10e– Br02  2BrV + 10e –

redox
equations Cl I + 2e–  Cl -I 5 Cl I + 10e – 5 Cl -I

balancing
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Oxidation-reduction (redox) reactions:
disproportionation reactions
(dismutation reactions)

(x+y) Aox1  x Aox1+m + y Aox1-n

x BAox1 + y CAox1  x EAox1+m + y FAox1-n

Cl20 + H2O HClIO + HCl-I

3KClVO3 + KClVO3  3KClVII O4 + KCl -I

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Introduction to electrochemistry: electrode, electrode potential

metal/H2O
metal ions

hydrated metal ions

equilibrium: M(s) = Mz+ + z.e-

+ + in the solution according to cz+

M
+ +
+ + Nernst equation – electrode potential
+ +
++ + R.T
E = E0 + ln cz+
M
Vel Vr Vr -Vel z.F
Faraday const. = NA.e 19
 Galvanic cells

Interrupted circuit
EMV = E2-E1 electromotoric voltage

In a closed circuit: electronic flow,

ion flow (electric current)  electric
work
Half cell Half cell
Galvanic cell

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 Standard electrode potentials

0.059
25°C  E = E0 + log cz+
M
z

Standard electrode potential: cz+

M = 1.00 mol L
-1

absolute n/a Reference electrode: H3O+/H2

Standard hydrogen electrode: E0 =0.0 V

1)  platinized platinum electrode

2)  H2 blow (1 atm)
3)  Solution of an acid [H3O+] = 1 mol L-1
4)  hydroseal for prevention of O2 intervention
5)  junction to the second half cell

H3O+ + e– = ½ H2 + H2O 21
Standard electrode potential: measurement

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 Standard electrode potentials

cathode
Metals with lower E0
reduce the cations of
metals with higher E0
non-noble

-1.18 eV

reducing ability
-0.13 eV

Mn+Pb2+  Mn2++Pb
Noble metals
Oxidation/reduction Electrode
(redox) potentials:

redox system +
indifferent (Pt)
electrode

reducing ability
Ox + z e– = Red

E = E0
0.059 [Ox]
+ z log [Red]

Nernst-Peters
equation
Example: H2O2 +2H++Sn2+  Sn4++2H2O
 Reverse process: Electrolysis

+
1.7-2.2 V
preferable
process
E = -0.41 V
[OH-]=10-7

E0=1.36 V E0= -0.83 V

Cl2(g) + 2e- → 2Cl-(aq)
2H2O(l) + 2e- → H2(g) + 2OH-(aq)
in progress:
Na+ (aq) + e- = Na(s) E0= –2.07 V
2Cl-(aq) → Cl2(g) + 2e-
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 Electrolysis from molten salts:

Cathode: Na+ + e– → Na(l) E° = –2.71 v

Anode: Cl– → ½ Cl2(g) + e– E° = –1.36 v Na

together: Na+ + Cl– → Na(l) + ½ Cl2(g) E° = –4.1 v

Al

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