] ][ ) ( [

] ][ ) ( [
6 2
2 5 2
1
L O H M
O H L O H M
K
z+
=

=
n
K
6

= ) log( ) log(
6 n
K
n z
m
z
n
n
L O H M
ML
] ][ ) ( [
] [
2
+
+
=
Summary inorganic chemistry part 1
Paragraph 6.11: Coordination complexes. In a Coordination complex a central atom or
ion is coordinated by one or more molecules or ions (ligands) which act as
Lewis bases (donates electrons), forming coordinate bonds with the central
atom or ion which acts as a Lewis acid (accepts electrons). toms in the
ligands that are directly bonded are called donor atoms. line is used to
denote the interaction between an anionic (negati!e ion) ligand and the
acceptor, an arrow is used to show the donation of an electron pair from a
neutral ligand to an acceptor. "he resulting species from a coordinate bond is
called an adduct. Can be indicated by a dot, e.g.# $%&'"$(.
)eutral complexes are usually sparingly soluble in water, but readily soluble in
organic sol!ents. "he p$ also has an e*ect, $
+
can compete for the ligand, and ,$
-
can act
as ligand.
Paragraph 6.12: Stability constants. .etal ions are often
hydrated, /.($0,)12
3+
is often written as .
3+
. 45uilibrium
constants (normally written without /$0,2 because that6s the
unity) for each displacement step (e.g. 78 depicted on the right
here) can be ta9en together by multiplying them (also see
right), resulting in the o!erall stability constant n. :sually
stability constant 7n decreases with increasing n (more ligands).
$ighly charged ions more negati!e ;hyd<
=
because they
impose more order on water, when highly charged ions form
complexes charge neutrali3ed (and also enthalpy signi>cantly
negati!e) ? ;@
=
substantially negati!e.
)umber of donor atoms through which ligand
coordinates is called denticity of ligand (mono-, didentate etc).
Aolydentates ? chelate ring (chelate from crab6s claw) with bite
angle B-.-C. 1 membered ring is stabili3ed D-bonding. <mall
metal ions fa!or 1 member rings, larger metal ions fa!or E
member rings. (..) Chelate complexes more fa!orable than
corresponding monodentate complexes (chelate e*ect). (..)
.acrocyclic ligands# a macrocylce is a cyclic macromolecule or
a macromolecular cyclic portion of a molecule.
O
B
H
H
H
Paragraph 19.2: Ground state e
-
congurations. .etals are elements that readily lose
electrons to form cations. F-bloc9 metals shown in image below. transition element (G d-
bloc9 metal) is an atom that has incomplete d-subshell or forms cations with incomplete
subshells. 4ach group of d-bloc9 metals consists of three members and is called a triad, >rst
and second row metals denoted by hea!ier. (irst, second and third row correspond
respecti!ely >lling %d, Hd, and Ed orbitals, from which there are howe!er minor de!iations.
.
0+
and .
%+
ions of >rst row metals all ha!e /r2%d
n
.
Paragraph 19.!: Physical properties. .etallic radii show little !ariation across a gi!en
row of d-bloc9, the >rst row metal is has smallest radii, the second and third are similar. "his
last fact is due to the lanthanoid (La (EI) J Lu (I8))contraction# the steady decrease in si3e
along the lanthanoid elements. .etals of d-bloc9 hard, ductile, malleable, less !olatile then s-
bloc9. ll %d metals ha!e !alues of I48 and I40 larger than those of calcium and all (except
3inc) ha!e ha!e higher !alues of Ka$
=
, which ma9e them less reacti!e than calcium. <ince all
9nown .
0+
ions of %d metals are smaller than Ca
0+
lattice and sol!ation energy e*ects are
more fa!orable for %d metal ions.
Paragraph 19.": #eacti$ity. .etals are moderately reacti!e. ,n thermodynamic grounds
metals should liberate $0 from acids, but generally do not either because passi!ation by thin
surface coating of oxide or because they ha!e a dihydrogen o!erpotential, or both. <il!er,
gold and mercury least reacti!e metals.
Paragraph 19.%: Characteristic properties. Colors are speci>c for species with other
ground state than d
=
and d
8=
and are pale because they6re against the Laporte selection rule#
e
-
transitions only if Kl L M8. .ore intenser colors originate from charge transfer absorptions
or emissions. 4BA)F NI"$ <4C"I,) 81.H.
(..) (paramagnetism). Intercon!ersion between oxidation states characteristic of d-
bloc9 metals. pparent oxidation state from molecular or empirical formula may be
misleading, e.g. La
%+
(I
-
)0(e
-
), sometimes metal-metal bonds or ambiguous oxidation states,
e.g. /"i(bpy)%2
n-
(n L =, 8, 0).
Paragraph 19.6: &lectroneutrality. Aauling6s electroneutrality principle estimates charge
distribution by assuming charge on single atom only -8 to +8. O
Co
NH
3
+
NH
3
+
NH
3
+
NH
3
+
+H
3
N
+H
3
N
3-
Co
H
3
N
N
H
3
NH
3
NH
3
H
3
N
H
3
N
3+
Co
NH
3
+
NH
3
+
NH
3
+
NH
3
+
NH
3
+
NH
3
+
3+
Co
NH
3
1/2+
NH
3
1/2+
NH
3
1/2+
NH
3
1/2+
H
3
N
H
3
N
1/2+
1/2+
conventional 100% covalent 100% ionic inbetween
Paragraph 19.': Coordination numbers. Coordination numbers and geometries are often
distorted from regular geometries, because e.g. steric e*ects. If there6s a small energy
di*erence between geometries, Puxional beha!iour in solution may be obser!ed.
In the 7epert model the metal lies at the centre of a sphere o!er which the ligands are
free to mo!e. "he ligands are considered to repel each other li9e Q<4AR, bot non-bonding
electrons are ignored, and the geometry is thus independent of the ground state e
-
con>guration. Common arrangement in the table on the right, not all are predicted by 7epert
because electronic factors or the inherent constraints of ligands. "ripodal ligands are ligands
containing three arms, each with a donor atom, originating from central atom or group which
also may be donor.
Coordination number 2. :ncommon, restricted only a few metal-ions (d
8=
). Coorindation
number 3. lso uncommon, also in!ol!ing d
8=
. <ome p-bloc9 ha!e t-shaped molecules
because stereochemically acti!e lone pairs, but not seen d-bloc9. Coordination number 4.
re !ery common, mostly tetrahedral# d
=,8,0,E,1,I,S,T,8=
. <5uare
planar if electronic factors strongly fa!or s5uare planar
arrangement, usually d
S
. Coordination number 5. "rigonal
bipyramid and s5uare based pyramidal. <ince small energy
di*erence often between extremes. Coordination number 6.
lmost always octahedral, but d
H
and d
T
tetragonally distorted# elongated or s5uashed. "his
octahedron trigonal pri!
is called the Uahn-"eller e*ect. lso a small group of d
=
and d
8
trigonal prismatic or distorted
trigonal prismatic en!ironment. Coordination number 7. 4arly second V third row (and also
lanthanoids and actinoids), rcation must be relati!ely large. In reality much distortion from
these structures. Coordination numbers 8, 9 and 10. (..)
Paragraph 19.(: )somerism. (..) (Read blue boxes).
Ligand
s
Geometr !bridi"atio
n
0 linear sp
% trigonal planar sp
0
H tetrahedralW sp
%
H s5uare planar sp
0
d
E trigonal bipyramidal sp
%
d
E s5uare based pyramidal sp
%
d
1 octahedral sp
%
d
0
I pentagonal bipyramidal sp
%
d
%
S dodecahedral sp
%
d
H
S s5uare antiprismatic sp
%
d
H
S hexagonal bipyrimidal X
T tricapped trigonal
prismatic
sp
%
d
E
Paragraph 2*.2: $alence bond
theory. Qalence bond theory
(hybridi3ation and o!erlap)#
hybridi3ation schemes can be used to
describe bonding d-bloc9 metals. &ut
!alence bond theory is !ery unrealistic
when trying to describe metal
complexes. <ee third electron
con>guration, where electrons are put unpaired in %d shell to achie!e diamagnetism (or high
spin) and Hd shell thus has to be used for hybridi3ation.
Paragraph 2*.!: crystal eld theory.
Ligands are considered points charges and
there are no co!alent metal-ligand interactions.
4lectrostatic >eld L crystal >eld. <ee >g. 0=.0,
if spherical approach ligands, all %d orbitals
would be raised. &ut octahedral approach# d30
and dx0-y0 raised more than dy3, dyx and d3x (the
closer the ligand, the greater the raise in
energy, - Y - repulsion). "he separation
energy is Koct, because the total energy remains the same, and two and three orbitals are at
the same energy le!el, energy is splitted =.1 and =.H Koct. .agnitude of Koct is determined by
the strength of the crystal field# Koct(strong field) Z Koct(wea9 >eld). Nith absporption
spectrum ion, e
-
promotion from t0g to eg (the resulting orbitals from splitting the d-orbital)
can be seen and Koct can thus be estimated. Koct determined by identity and oxidation metal
and nature of ligands. Koct depends on ligands as follows#
"
L
L
L
L
L
L
n+
#
$
%
/wea9 field# Koct[2 I
\
] &r
\
] <
0\
] <C)\ ] Cl
\
] ),%
\
] )%
\
] (
\
] ,$
\
] C0,H
0\
] $0, ]
)C<
\
] C$%C) ] py (pyridine) ] )$% ] en (ethylenediamine) ] bipy (0,0^-bipyridine) ] phen
(8,8=-phenanthroline) ] ),0
\
] AAh% ] C)
\
] C, /strong field# Koct_2
<ame donor atoms close together. Koct !aries irregularly
across the first row of the d-bloc9. (or metals, Koct
decreases down triad, spectrochemical series of metals
can be made independent of ligands#
/wea9 field# Koct[2 .n(II) ] )i(II) ] Co(II) ] (e(III) ] Cr(III)
] Co(III) ] Ru(III) ] .o(III) ] Rh(III) ] Ad(II) ] Ir(III) ]
At(IQ) /strong field# Koct_2.
Ko increases with oxidation state.
Ko decreases within group
(or a gi!en d
n
con>guration the crystal >eld stabili3ation
energy (C(<4) is the di*erence in energy between the d
electrons in an octahedral crystal >eld and the d electrons if they would be located in a
spherical crystal >eld.
"his depends on Koct and A. A is the electron-pairing energy, the energy it costs to put
two electrons from parallel spin to spin-paired. "his energy is comprised of the (loss of)
exchange energy and the coulombic repulsion between the spin paired electrons. 4xchange
energy (see orbital image right)# di*erence both electrons parallel
spin (more stabile) and re!erse spins.
4lectrons can be put in the two splitted orbitals low spin or high spin. In low spin
the lowest orbitals gets >lled completely >rst, and in high spin the aufbau principle goes for
all orbitals. "he electrons will >ll the orbitals creating the lowest C(<4, which is thus#
C(<4 L (nlow) ' Koct,low + (nhigh) ' Koct,high J A
`#$ere % is t$e & o' (aired in )om(arison #it$ s($eri)a* +e*d,
$ence, or loo9ed upon differently, if Koct Z A (strong crystal
>eld) it costs more energy to put the electron in the high
energy orbital (eg) than paired in the lower t0g orbital, the
complex will thus be low spin. "he other way around# if Koct ] A (wea9 crystal >eld), it is more
energy eacient to put the electrons in the higher orbital (eg) >rst, if these are empty.
-a$n./e**er distortions. Uahn-"eller distortions originate
if electron density is not e5ually distributed. "he
metal-ligand bond lengths are stretched if nearby
orbitals are >lled and !ice !ersa (see image), leading
to a distortion. "his is often the case in octahedral d
H
and d
T
complexes.
/$e -a$n./e**er t$eorem states t$at an non.*inear mo*e)u*ar sstem in a degenerate
e*e)troni) state #i** be unstab*e and #i** undergo distortion to 'orm a sstem o' *o#er
smmetr and *o#er energ, t$ereb remo0ing t$e degenera).
/etra$edra* )rsta* +e*d. dxy, dy3, dx3 orbitals nearer to ligands than
d30 and dx0-y0. Ktet L
H
bT'Koct, because Ktet is smaller, tetrahedral
complexes are high spin. lso di*erent colours. In (e,H
H-
Uahn-
"eller distortions lead to di*erent bond angles.
12uare (*anar )rsta* +e*d. Can be deri!ed by remo!ing two trans ligands from an
octahedral con>guration. 4.g. from 3-axis, d30 greatly stabili3ed, dy3 and dx3 (also
point partially in 3-direction) also stabili3ed, dx0-y0 is massi!ely destabili3ed, whereas dxy is
moderately destabili3ed. /)iClH2
0-
is tetrahedral, while /Ad(II)BH2
3-
and /At(II)BH2
3-
are both
s5uare planar, because Ad and At (0
nd
and %
rd
row) cause larger crystal >elds.
3t$er )rsta* +e*ds. <ee image on next page, though only for li9e ligandsc
Fe
(IV)
O O
O O
125&
12'&
(-
+ctahedral Pentagonal bipyramidal S,uare antiprismatic
S,uare planar S,uare pyramidal -etrahedral
-rigonal bipyramidal
Paragraph 2*.": .olecular orbital theory. .olecular orbital theory o*ers alternati!e for
the crystal >eld theory. (irst ta9e a loo9 at d%.0 and pp 8=T.
Paragraph !.2: Symmetry operations / elements. symmetry operation is an
operation which lea!es it in a con>guration that is indistinguishable from its original
con>guration. "he operation is carried out with respect to symmetry elements, i.e. points,
lines or planes. "he symmetry operation around an n-fold axis is noted by Cn, n-fold meaning
that a (%1=ebn) rotation leads to the same con>guration. If a molecule possesses more than
one axis, the axis with the highest n-!alue is called the principal axis. <ometimes di*erent
order axes coincide (e.g. CH with C0 in s5uare planar).
Reflection through a plane is denoted with the f symbol. If the plane is perpendicular
to a Cn axis, it is labelled fh (hori3ontal) and if it coincides with the principal axis it is labeled
f! (!ertical). f! refers to the plane bisecting the ($-,-$) bond and f!6 refers to the plane in
which the molecule lies. fd (dihedral) label is gi!en if the plane bisects an angle between
two Cn axes.
"he center of in!ersion is the point from which you can draw an in>nite number of
straight lines such that each line passes through (a) pair(s) of similar points, one on each
side of the centre of symmetry and at e5ual distance from it.
rotation followed by a rePection through a plane perpendicular to that axes, which
is called the improper rotation axis, resulting in the same con>guration, is designated with
<n.
ll obgects can be operated upon by identity operater 4, which lea!es the molecule
unchanged, all elements are thus at least said to ha!e the symmetry element 4.
Page 1*9: 0 bent triatomic: 12+. <ymmetry can be used in di*erent ways, a short
example follows.
C20 4 C2 50(6") 507(")
8 8 8 8 8
0 8 8 -8 -8
&8 8 -8 8 -8
&0 8 -8 -8 8
It is possible to de!elop an ., picture of the $0, bonding based upon symmetry information.
"he C0! character table is shown abo!e# labels in the >rst column under the point group
symbol tell us the symmetry types of orbitals that are permitted within the speci>ed point
group. point group is a set of symmetry operations forming a mathematical group, for
which at least one point remains >xed under all operations of the group
8
. "he numbers in the
4 column indicate the degeneracy of each type of orbital, in the C0! point group all orbitals
ha!e a degeneracy of 8, i.e. they are non-degenerate. "he rows of numbers following a gi!en
symmetry label indicate how a particular orbital beha!es when operated by each symmetry
operation# 8 means unchanged, -8 means it changes sign, = means it changes in some other
way. (or example# the 0s orbital remains unchanged by all symmetry operations (resulting in
only ones), and is as de>ned in the character table gi!en the label a8 (lower case, only in
the table uppercase letters are used).
8
http#bben.wi9ipedia.orgbwi9ib.olecularhsymmetryiAointhgroups
1mb
o*
3(eration 4*ement 46am(*e
Cn Rotation n-fold axis
(%1=ebn)
f RePection Alane
i Centre
<n Rotation + rePection through a
plane perpendicular to the axis
n-fold improper
rotation axis
Paragraph 2*.": .olecular orbital theory 2continued3. ., theory does consider
co!alent interactions in complexes.
83 t$eor (based on )$a(ter 4 9 ( 120: 1;6)
., theory compares symmetries to establish a molecular orbital diagram. (or example, a
>rst row metal has %d, Hs and Hp !alence shells. "hose can be di!ided in di*erent
symmetries.
Hs a8g symmetry
Hp t8u symmetry
%dx0-y0, %d3 eg symmetry
%dxy, %dy3, %dx3 t0g symmetry
It is 9nown that only p orbitals of the ligands interact with the metal.
.ore precise, only the p3 orbitals (if each ligand is gi!en its own axis
set). (urthermore, from an examination of how many of these p orbitals
are the same after ,h symmetry operations it can be concluded that
the L@, is a sum of 8g, "8u and 4g symmetries. 1 new wa!efunctions
can thus be deri!ed by mixing the p orbitals.
"o construct the ., diagram, orbitals of same symmetry are
mixed. ,rbitals with another symmetry become non-bonding
orbitals. Fisplayed to the left an image of bonding in <(1. < only has
s V p orbitals.
5.bonding on*. (or an octahedral metal-ligand complex an ., diagram can thus be
constructed, each ligand beha!es similar to the aforementioned Puor. "he metal has >!e %d
orbitals (eg and t0g), a Hs orbital (a8g) and three Hp orbitals (t8u). "his leads to the following .,
diagram#

"here is greater o!erlap between the metal s and p orbitals and the ligand p orbitals than
between the metal %d and the ligand p, which leads to more stabili3ation. If there is no D
bonding, the energy le!els between t0g and eg` correspond with Koct. ,b!iously, if the eg, t8u
and a8g orbitals are >lled (which can be done by the electrons supplied by the ligands), the
remaining electrons (from the metal) are di!ided depending on wea9 or strong >eld, gust as
in the crystal >eld theory.
Com(*e6es #it$ < bonding a*so. <ometimes D bonding considered for d t0g orbitals (dxy, dx3,
dy3) and ligand d orbitals in the case of phosphine ligands (e.g. AR% or A(%), but more often
other interactions. I.e. ligand f`-orbitals as acceptor orbitals. "here are two types of ligands#
D-donor and D-acceptor ligands.
- a D-donor ligand donates electrons to metal
centre in an interaction that in!ol!es a >lled
ligand orbital and an empty metal orbital.
- a D-acceptor ligand accepts electrons from
the metal centre in an interaction that
in!ol!es a >lled metal orbital and an empty
ligand orbital.
D-acceptor ligands can stabili3e low oxidation state metal complexes.
<.donor
*igands
<.a))e(tor *igand
Cl
-
, &r
-
, I
-
C,, )0, ),

Nhen a metal is bound to a D-donor ligand, the t0g orbitals will not be split !ery far. Nhen a
metal is bound to a D-acceptor ligand, the splitting will be much more. <ee diagrams abo!e.
lso, when the metal is bound to a D-donor ligand, these orbitals will bring in more
electrons, thus changing where the metal electrons will go (mar9ed light greenW the rest is
>lled with bonding electrons, in case of donor thus also donated electrons). "he number of
bonding electrons is always the same in the two separate cases respecti!ely, the number of
metal electrons can change# in f-complexes there are 80 electrons from the ligand and in D-
complexes the f and D orbitals from the ligand contribute 8S electrons (1`0f + 1D). "hese
can be considered to >ll the orbitals below the green orbitals (see picture).
(or better, but still 5ualitati!e pictures, see p. E1S boo9. $owe!er, conclusions can be
drawn#
- Koct decreases in going from f-only complex to f- and D-complex (compare abo!e
donor picture to picture on pre!ious pageW and bare in mind that eg` stays e5ual).
o (or a complex with D-donor ligands, increased D-donation (X) stabili3es t0g le!el
and destabili3es t0g`, thus decreasing Koct.
- Koct !alues are relati!ely large for D-acceptor ligands, and those complexes are thus
li9ely to be low spin.
o (or a complex with D-acceptor ligands, increased D-acceptance stabili3es t0g,
increasing Koct.
(urthermore, since >lling antibonding orbitals is detrimental for complex-formation,
octahedral complexes with D-accepting ligands will not be fa!oured by d
nZ1
. n obser!ation
can be made that d-bloc9 metals tend to obey the e*ecti!e atomic number rule or the 8S-
electron rule. <ee also chapter 0%# low oxidation state organometallic complex contains D-
acceptor ligands and the metal centre tends to ac5uire 8S electrons in its !alence shell (the
8S-electron rule), thus >lling the !alance shell. "he 8S-eletron rule is useless for higher
oxidation state metals, can be rationali3ed by smaller energy seperations. ,ther complexes
than octahedral fall out of the scope of this discussion (see p. EI=).
(..W some exceptions for ),).
Paragraph 2*.%: 4igand eld theory. Non6t go in to mathematics of ligand >eld theory,
howe!er, ligand >eld theory is an extension to crystal >eld theory which is freely
parameteri3ed (as opposed to locali3ed >eld from point charge). It is also con>ned to d
orbitals. part from Koct it also uses Racah parameters which are obtained from electronic
spectroscopic data.
Paragraph 2*.6: &lectronic spectra. bsorptions arise from transition between electronic
energy le!els#
- "ransitions between metal-centred orbitals possessing d-character (jd-d6 transitions).
o Nea9er.
o Can be mas9ed due C" transition.
- "ransitions between metal- and ligand-centred .,s which transfer charge from metal
to ligand or !ice !ersa.
o .ore intense.
o .LC"# metal-to-ligand charge transfer
o L.C"# ligand-to-metal charge transfer
k is wa!elength, l is propagation speed en c is the speed of light, is the
wa!enumber.
bsorptions are relati!ely fast in comparison to molecular !ibrations and rotations (with
which the energy le!els change), hence, the obser!ed absorption fre5uencies !ary. "here is
an absorption maximum kmax (nm), with corresponding max (absorbance), kmax is used to
describe the particular band. "he molar extinction coefficient (a9a molar absorpti!ity) mmax#
Nhere mmax is the molar extinction coeacient, max the maximum absorption (n
kmax), c the concentration, and l the pathlength (in cmc) of the spectrometer
cell.
c

= =
1

=
c
A
!a%
!a%

)ote (without explanation) that#

- d
8,H,1,T
complexes consist of one absorption.
- d
0,%,I,S
copmlexes consist of three absorptions.
- d
E
complexes consist of a series of wea9 but sharp absorptions.
1e*e)tion ru*es.
<pin selection rule# ipairedbunpaired electrons stays e5ual. <pin 5uantum number
< doesn6t change (K< L =).
Laporte selection rule# ,rbital 5uantum number l has to change with 8# Kl L = (e.g. s?s
and p?f forbidden).
"hese selection rules are strict, but exceptions occur under speci>c conditions (see p. EI8)#
/(e /(i)a* =ma6
<pin forbidden, jd-d6 ]8
Laporte forbidden, <pin allowed jd-
d6
8-8= (centrosymmetrisch),
8= -8=== (niet
centrosymmetrisch)
Charge transfer (fully allowed) 8=== - E= ===
Paragraph 2*.(: .agnetic properties. Aaramagnetism arises from
unpaired electrons. 4ach electron has a magnetic moment with one
component associated with spin angular momentum of electron, and a
second component associated with the orbital angular momentum
(except when l L = (s)). "he image to the right depicts momenta,
howe!er, this is not realistic, spins are not real.
(or many d-bloc9 complexes the orbital momentum can be ignored, and the magnetic
moment o can be determined from the number of unpaired electrons#
) 2 ( ) 1 ( 2 + = + = n n S S
Nhere < L total spin 5uantum number and n L unpaired electrons (< L
n
b0).
4ffecti!e magnetic moment, oe*, can be obtained from experimentally measured molar
magnetic susceptibility, pm. "he oe* can be determined from pm as follows#
T
L
T k
m
B
m
eff

')'' * 0
3
2
0
= = (for <.I. units).
9 L &olt3man, pm L magnetic susceptibility, " L temperature, L L !agadro number,
o= L !acuum permeability, o& L &ohr magneton (see p. EIT).
4.g. a @ouy balance# sample is hung in balance and magnetic >eld
applied to it, sample mo!es and di*erence in weight can be read
out, from which magnetic susceptibility, pm, can be determined.
;erromagnetism, anti'erromagnetism and 'errimagnetism. If metal
centres are separated by diamagnetic species, they are said to be magnetically dilute.
Nhen paramagnetic species are close together (bul9 metal), or separated by species able to
transmit magnetic interactions (as many d-bloc9 oxides, Puorides and chlorides are), the
metal centres can couple (interact). "his may gi!e rise to ferromagnetism or
antiferromagnetism.
In a ferromagnetic material, large domains of dipoles
are aligned in the same direction. In an
antiferromagnetic material, neighbouring magnetic
dipoles are aligned oppositely. bo!e the Curie
temperature ("c) the thermal energy is suacient to
o!ercome the alignment. ntiferromagnetism occurs
be*o# the )qel temperature (")). (errimagnetism
occurs when relati!e !alues of momenta are di*erent.
Nhen a bridging ligand facilitates coupling of
electron spins on adgacent metal centres, this
happens by super-exchange. "he two metal centres
(in image on the left and right) interact with two
spin-paired electrons in the same orbital of a ligand. <ince these are spin paired, and the
con>guration in the ., also has to be spin-paired, the result is an anti-parallel coupling of
the two metal centres.
Paragraph 2*.9: ligand eld stabili5ation energies 246S&3. L(<4 terms are only small
parts of total interaction energy. $owe!er, going to the di*erent d
n
con>gurations, it shows
remar9able similarities with other thermodynamic energy trends, such as lattice energies
and hydration enthalpies of metals. Fe!iation from the dotted line may thus be ta9en as
measures of thermochemical L(<4 !alues. @enerally L(<4 !alues are in compliance with
Koct !alues measured from electronic spectroscopy.
s can be seen the >gure abo!e, d
=,E,8=
complexes should
not fa!our octahedral or tetrahedral con>gurations.
$owe!er, other factors should be ta9en into account. 4.g.
the smaller si3e of tetrahedral complexes results in
higher lattice and sal!ation energies, hence, for example
)i
0+
(d
S
) does not form tetrahedral complexes in a5ueous
solutions, only in melts or non-a5ueous media.
(..W !erhaal o!er spinels).
Paragraph 2*.1*: -he )r$ing-7illiams series. In a5ueous solutions, water is replaced by
other ligands, and the position of this e5uilibrium will be related to the di*erence between
the two L(<4s, since Koct is ligand-dependent. "he stability constants howe!er show the
following single-hump#
.n(II
)
] (e(II
)
] Co(II
)
] )i(II
)
] Cu(II
)
Z rn(I
I)
d
E
d
1
d
I
d
S
d
T
d
8=
"his is not in accordance with the L(<4 energies (that pea9 at d
S
), but this can be explained
from the fact that L(<4 is not the only contributing factor. Ionic radii should also be ta9en into
account, these ha!e the following trend#
.n(II
)
Z (e(II
)
Z Co(II
)
Z )i(II
)
] Cu(II
)
] rn(I
I)
d
E
d
1
d
I
d
S
d
T
d
8=
(Lattice energy)
"his trend can also be explained by dependency on d
n
con>gurations (and not only on the re*
increment leading to a decrease in radius). $owe!er, this trend also doesn6t explain the
stability of copper. Copper is !ery stabile because a d
T
complex has a Uahn-"eller distortion.
"his also renders the image of a >xed ionic radius useless. ppearantly in this distortions H
stronger bonds compensate for the 0 wea9er (longer) bonds in such a way to ma9e it more
stabile than )i(II).
Paragraph 2*.11: oxidation states in a,ueous solutions. 4
=
!alues (..W nog le3enc- na
deel 0).
+o8 nog doen:
- Chelaat e*ect meer uitleg `3ie %S