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(complex)
complex: used by chemists for compounds that consist of
(several) other compounds that can exist separately
1
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)
3
chelate complexes
EDTA
Ethylendiamin
(en) Ethylendiamintetraacetate(4-)
bridging ligands
4
Coordination compounds: bonds/structure
trans-
cis-
geometrical isomers
e.g. cis-[PtCl2(NH3)2] trans-[PtCl2(NH3)2]
diammin-dichloridoplatinum(II) complex
5
Typical space structures of complexes
Trojnásobne zastrešená
Trigonálny dodekaéder trigonálna prizma
6
Geometrical isomerism for octahedral structures
8
paramagnetic [NiCl4]2- unpaired electrons
Ni(II) -[NiCl4]2–
sp3
High-spin complex
Ni2+
28Ni
3d 4s 4p
9
diamagnetic [Ni(CN)4]2- paired electrons
Ni(II) -[Ni(CN)4]2–
dsp2
valence Ni2+
Ni2+
Ni
3d 4s 4p
Low-spin complex
10
Coordination compounds: bonds/structure
??????
metal-ligand bond is weaker than „usual“ covalent b.
MO theory
simplified approximations
11
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
12
Why the transition metal complexes are colored?
octahedral
eg
Energy
t2g
t2
Δ
Energy
d
e
13
low and high-spin complexes [Fe(CN)6]3- [FeF6]3-
eg
Δ
Δ
t2g
Fe3+
Fe0
5d 4s
15
Relative ligand field strengths
Spectrochemical series
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Oxidation-reduction (redox) reactions: change of oxidation state
balancing
17
Oxidation-reduction (redox) reactions:
disproportionation reactions
(dismutation reactions)
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Introduction to electrochemistry: electrode, electrode potential
metal/H2O
metal ions
Interrupted circuit
EMV = E2-E1 electromotoric voltage
20
Standard electrode potentials
0.059
25°C E = E0 + log cz+
M
z
H3O+ + e– = ½ H2 + H2O 21
Standard electrode potential: measurement
22
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
Al
26