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Lect-12
Preliminaries/Background
Just as element names/symbols were memorized for FRO8 atoms
(Li, Be, B, C, N, O, F, Ne), now you are asked to memorize the FROTM
atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn). These elements provide most of the examples
for (1) main group chemistry and (2) now TM chemistry, so we need to be very familiar with
their names, symbols, and ground state and ion electron configurations, and term states.
2
FROTM have vse configurations of 4 s 3d . The 4 s electrons are first lost, so all
TM elements have a common + 2 ox.st. (In the FROTM only copper has a + 1ox.st., and in
later rows silver and gold.) Many TM atoms also display + 3 and higher ox.sts., when 3d
electrons are removed.
Angular Distribution Diagrams of d atomic orbitals Reacquaint yourselves with names,
shapes, locations and trigonometric signs of d atomic orbitals. (d orbitals are gerade)
d xy four lobes in the XY plane and between X and Y axes
d xz
d yz
dx y
dz
2
dn
term symbol
d1
d2
d3
d4
d5
d6
d7
d8
d9
d 10
( ) involves the
( L) as shown:
( S + L )
where g is the gyromagnetic ratio (which has a value very close to 2), and
S = ms and L = ml
8
Apply this expression to the
Ni(II) = d
case of Ni(II) ion, and compare
to the experimental magnetic
moment of 2.83 Bohr Magnetons
S =2/2
ml =
-1
-2
( S + L) = 4.5 B.M.
L =3
This does not compare well with the experimental value. A modification of this
expression suggests that for lighter metals (like FROTM) the contribution of the spin
term is more important than the orbital term. This leads to a spin-only formula:
( spin only ) = 2 S ( S + 1)
or equivalently
n = number of unpaired electrons. For Ni(II) ( so )
( so ) = n( n + 2)
where
( so )
Magnetic moment determinations are important because they afford a means of (1)
COUNTING unpaired electrons by using experimental ( so ) value and calculating n
from the above expression, and (2) determining the oxidation of the TM.
Some Examples of Science "in Action"
First, accumulate sets of information, and
then analyze for trends and/or anomalies.
Consider several examples:
a.
configurations of ns and np ,
This information is analyzed
and intepreted to show very stable electron configurations at (2), (2)+(2+6),
(2)+(2+6)+(2+6), and (2)+(2+6)+(2+6+10)+(2+6) electrons.
b.
c.
d.
The questions are posed. Let's begin looking for answers (and finding understanding).
transformation properties of
2
dz
and
dx y
2
L1
+z
L2
TM
L6
+x
L3
+y
L5
L4
Sigma-bonded Oh TM Complexes
Transformation properties of sigma-bonding p-type atomic orbitals for six ligands
Using methods met and used in Chapter 5, ligand -bonding orbitals transform as
( bonds ) = a1 g + eg + t1u
the eg symmetry orbitals, i.e.,
d z and d x y of the TM.
The TM d xy , d xz , d yz are
2
t2g
non-bonding in this case. The MO
diagram for a sigma bonded Oh TM
complex is shown as Figure 10-5 on
page 321. Isolation of TM d orbitals from this diagram shows the above pattern. The
eg and t2 g
and is represented by the arrow in the above diagram. The MAGNITUDE of the
energy difference
varies, depending on (a) inherent bonding strength of the
ligand, and (b) charge of the TM ion.
t2 g
eg
set (two
Or,
2 x (destabiliz ) + 3 x ( stabiliz) = 0
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particular d configurations will be more (or less) favored for Oh complex formation.
Refer to text Table 10-5 on page 325, and the following development
d 1 [as in Ti(III)]
d 2 [as in Ti(II),
V(III) ]
d 3 [as in V(II),
Cr(III) ]
Two situations arise for d 4 through
When energy of
is small, relative to energy required for electron pairing, then a
WEAK FIELD (with respect to ligand bonding strength) or HIGH SPIN (with respect to
number of unpaired electrons) condition prevails and so the maximum number of
unpaired electrons will be present.
When energy of
is large, relative to energy required for electron pairing, then a
STRONG FIELD
d 4 [as in Cr(II),
Mn(III) ]
Notice that the d weak field case results in FOUR unpaired electrons, but the strong field
case has only TWO unpaired electrons. So measurements of magnetic moments can be
used to identify and distinguish between strong field and weak field ligands and complexes.
5
Convince yourself that the following results would be obtained for d , d , d cases
[ WEAK FIELD ] LFSE
n
[ STRONG FIELD ]LFSE
5
d
d6
d7
-10/5
-2/5
-12/5
-4/5
-9/5
d vse, only weak field cases are possible so they would be as indicated below.
d8
-6/5 2
and
d9
-3/5
1
6
5
LFSE are largest for d in a strong field, and zero for d in a weak field. This information can
For 8 and 9
be used to account for some observations in the accumulated data presented at the beginning
d 6 strong
5
Mn(II) and Fe(III) have lowest hydration energies, and they both are d weak field
of the hour: Co(III) has the largest hydration energy , a nd its aqua complex is a
field case.
cases having LFSE = 0.
Magnetic moments are very informative in identifying ox.sts. and field strengths of complexes.
Consider some information about iron complexes. Octahedral complexes of Fe(II), a
can be strong field/low spin with n =0, or weak field/high spin with n =4. Octahedral
5
d 6 case,
Pi-bonded Oh TM Complexes
Carbon Monoxide, a pi-acceptor ligand.
Consider the mo diagram for CO, a ten
electron system.
2p
2p
2s
2s
O
Energy of the empty pi* LUMO is
similar to that of the TM d vse, and more
importantly, they are symmetry matched, so
bonding between them is possible. In this instance however, the TM furnishes
electrons to the empty pi* LUMO, in a manner known as "back-bonding".
The combination of a sigma bond (donation from C in CO to the TM) and pi-bond (backbonding from TM to empty pi* LUMO in CO) makes for exceptionally strong net
bonding. This is the reason for the toxicity of CO; it binds so strongly to heme iron in
blood that oxygen can no longer be processed. Cyanide anion is isoelectronic with CO
and is also an excellent pi-acceptor ligand. Pi-acceptor ligands are strong field ligands.
Compare CO and CN 1 - to chloride anion, Cl 1 - . Chloride anion has a complete octet
of vse; all of its vs are filled so it cannot accept (pi) electrons from TM. However, it can
donate pi electrons to the TM. But the TM in a complex is already in enough trouble
w/r to electrons and doesn't need any more. Consequently, pi-donor ligands like
chloride anion are weak field ligands; they present too much electron density to the TM.
(3)
o values)
MODERATE FIELD
NO 2
1-
en
NH 3
H2 O
1-
WEAK FIELD
RCO 2
1-
OH
1-
Cl
1-
Br
1-
1-
pi-donor ligands
D4 h
transformation properties of
2
+z
y axes.
Clearly the
dx y
2
L4
would be
+x
d yz
L3
TM
+y
L1
L2
b1g
1,3
7,8
b2g
5,6
a1g
2,4
eg
Td
transformation properties of
2
or
u subscripts.
t2
e
The energy difference between the two levels is labeled t and is represented by the arrow
in the diagram. A Td field is less than an Oh field because there are only four donor atoms
instead of six. It can be shown that
4
t o .
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