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METALLIC BONDING
Delocalized valence electrons are responsible for high thermal and conductivities of
metal
Band theory
N atomic orbitals are combined to
Band: continuum of energy levels
form N molecular orbitals, half of
which are bonding molecular orbitals,
the other half, antibonding molecular
orbitals
The larger N the more molecular
orbitals that are formed and the closer
in energy the bonding and
antibonding become
Metals are characterized by having a band Difference b/w semiconductors, metals and
structure in which the highest occupied
insulators depend on:
band is partially filled
Band structure
Valence bands are full/partially filled
Magnitude of energy gap b/w full and
empty bands
Insulators: band gap is very large; very
n-type semiconductors: more valence
few electrons have sufficient thermal
electrons than silicon
energy to be promoted to the empty band
above
p-type semiconductor: less valence
electron than silicon
Semiconductors: band gap not as large;
a few electrons have sufficient thermal
energy to be promoted; hence
conductivity increases with increasing
temperature.
Electrons that are promoted into
conduction band are regarded as
negative charge carriers. The vacant
electron levels left behind are called
positive holes
Cu-4s1 3d10
Zn- 4s2
Co-ordination Compounds:
Coord
Geometry
no.
6
Octahedral
4
Tetrahedral or square planar
2
Linear
2+
Pt always forms square planar complex,
Pd2+nearly always and Ni2+sometimes.
Ligands:
Unindentate: single donor atom (one pair
of e-)
Bidentate: two donor atoms (2 pairs of e-).
If both donor atoms are bound to the same
metal ion, they are called chelate.
Polydentate:3 or more donor atoms
Ionization energies:
Generally increase going across the period
.
I3 increases more rapidly than I1.
Standard reduction potential:
All of the first row transition metal except
copper can reduce H+ ion to hydrogen gas
in 1M solutions of strong acid.
Reducing abilities generally decrease
across the period
Sc>Ti>V>Mn>Cr>Zn>Fe>Co>Ni>Cu (Cr
and Zn do not follow this trend.
Structural isomerism:
1. Ionisation isomerism eg.
CrSO4(NH3)5Br and . CrBr(NH3)5SO4
2. Co-ordination eg. Cu(NH3)4PtCl4
and Pt(NH3)4CuCl4
3. Linkage eg. CoCl(NO2)(NH3)4Cl and .
CoCl(ONO)(NH3)4Cl (different point
of attachment
Atomic radii:
Generally decrease across the period.
There is a significant increase in size from
1st to 2nd row but not to the 3rd due to
Lanthanide contraction
d-electrons effect
The d-electrons are inner electrons and as
such do not as readily participate in
bonding as electrons in s and p valence
orbitals.
The d electrons do influence the
coordination number of the metal ion and
changes in the energy level of the delectrons are responsible for such
properties as the colour and magnetism of
the complexes.
hybridization
The colour and magnetism result
from changes in the energies of the
the d orbitals on the metal ion cause
by metal-ligand interaction.
Crystal Field Theory (CFT)
Focuses on the relative energies of the d
orbitals in transition metal complexes.
Assumes that ligands can be
approximated by negative point
charges and the metal-ligandbonding is entirely ionic.
The splitting of the energies of 3d
orbitals explain the colour and
magnetism of complex ions of the 1st
row transition metal ions.
Centre of gravity rule: in a purely
electrostatic field the pattern of
splitting is such that the algebraic
sum of all energy shifts of all orbital
is zero.
Weak field/high spin: arises when the
splitting of 3d orbitals is relatively small,
whereby the 3d electrons occupy both the
t2g and eg sets before pairing can occur
(Hunds rule) (yields max no. of unpaired
electrons) -> diamagnetic
Studies on many octahedral complexes containing 1st row transition metal ions have
shown that ligands can be arranged in order of their ability to produce splitting of the
energies of the 3d orbitals.
Spectrochemical series: CO>CN->NO2-> en(ethylenediamene)>NH3>py>NCS>H2O>OH->F->Cl->SCN>Br>I (the order is from large 0 to small 0)
-the magnitude of 0 for a ligand increases as the charge on the metal ion increases
-the largest P is found for the d5 configuration and hence complexes containing a d5
metal ion eg. Mn2+ or Fe3+ are exceptionally stable in the high spin state.
-nearly all Co(III) complexes on the other hand have low spin configuration (except
CoF63- )
-complexes containing divalent (valency of 2) 1st row metal ions are typically high spin
Tetrahedral Complexes
Colour of 1st row transition metal
d0 VO2+ yellow, Cr2O72- orange, CrO42- yellow,
None of the d orbitals point towards
MnO4- purple
the point of charge ligands in a
d1 Ti(H2O)63+ purple, VO(H2O)52+ blue
tetrahedral complex.
The t2 set are closer to the negative
d2 V(H2O)63+ blue-green
poin tin charge than the e set. Hence d3 V(H2O)62+ violet, Cr(H2O)63+ violet
the t2 set occur at higher energy.
d4 Cr(H2O)62+ sky blue
t is small hence invariably high
spin,
t =4/90
Favoured if the central atom is small
or the ligands large for then the
steric effects override the energy
advantage of forming metal-ligands
bonds.
Intensity of colour:
A = cl
A= absorbance
= absorbance coefficient (m2mol-1 )
c = concentration of the solution (mol/L)
l = path length (cm)
Jahn-Teller Distortion
Many octahedral complexes have a
distorted geometry whereby two axial
bonds are longer or shorter than the other
four. Distortion from a regular octahedron
is termed tetragonal.
Jahn-teller effect is a manifestation of
the theorem: a non-linear molecule in a
degenerate electronic state will be
unstable and will undergo a geometrical
distortion which lowers its symmetry and
splits the degenerate state.
If orbitals are unsymmetrically
occupied the resulting repulsion will
be unsymmetrical and hence some
ligands will be able to approach
closer to the metal ion than the
others and hence a distorted
geometry.
Largest distortion expected when eg
set is unsymmetrically occupied as
these orbital point directly towards
the negative point charge ligands.
Distortion increases the energy of
stabilization of the octahedral
complex.
Largest for h.s. d4, l.s. d7, d9
Linear complexes
Aligned along the z axis which means
the dz2orbital is the highest energy
orbital. The other d orbitals are
divided into two pairs of degenerate
orbitals: dxz and dyz and the dx2-y2 and
dxy orbital, the latter pair being the
lowest in energy.
Typically formed by d10 ions