enables us to produce

a complete
of their
orbital
structure.
case letters
will be description
reserved for the
different
irreducible
representat
enables
us to produce a complete description of their orbital structure.
terms.

2a1g
2t1u
p t1u
p t1u

s a1g

2eg
2a1g
2a1g

character tables, for the symmetry of electronic states and for spectro
Comment
terms.
Comment
In what follows, the symmetry of atomic or molecular orbitals will be
2a1g
In
what follows,
symmetry
of atomic
orbitals will be
, emolecular
represented
with the
lower-case
letters
(a1g , t1uor
g , t2g , etc.), while upper, eg , t2g , etc.),
while upperrepresented
withbelower-case
letters
(a1g , t1uirreducible
case letters
will
reserved
for
the different
representations
in
2.1.2.3.
Interaction
diagram
2t1u
case
letterstables,
will be
for theofdifferent
irreducible
in
character
forreserved
the symmetry
electronic
states andrepresentations
for spectroscopic
Interaction
diagram
We character
can now2.1.2.3.
construct
allsymmetry
the MOof
ofelectronic
an octahedral
complex,
by allowtables,
for the
states and
for spectroscopic
terms.
Fundamento ding
e la
r
egla
d
e
l
os
1
8
e
lectrones
the metal
2.2,
left-hand
to interact
with by
terms.
We orbitals
can now (Figure
construct
all the
MO ofside)
an octahedral
complex,

La regla de los 18 electrones

the symmetry-adapted
combinations
of orbitals
on the side)
six ligands
ing the metal
orbitals (Figure
2.2, left-hand
to interact
(Figure 2.2, right-hand
side).
the symmetry-adapted
combinations of orbitals on the six li
2t1u
The energetic
adopted
for the metal orbitals follows the
(Figureordering
2.2, right-hand
side).
2t
t2g1u
et1u
p
g
2.1.2.3.
Interaction
diagram
d t
usual ruleInteraction
for the
transition
< metal
(s) orbitals
< (p)follow
2g
The d-block
energetic
ordering metals:
adopted (d)
for the
p t1u
2.1.2.3.
diagram
t2g
eg
d t
(Chapter
1, usual
1.4.2).
sixMO
ligand-orbital
combinations
are
not
all <
We
can now
construct
all
of an octahedral
complex,(d)
by allowruleThe
forthe
the
d-block
transition
metals:
< (s)
2g
Aceptor
We
can
now
construct
MO2.2,
of
an
octahedral
complex,
alloweg
s a1g
at the
energy.
To1,all
understand
the
energetic
ordering
in by
Figure
2.2,are n
ing
thesame
metal
orbitals
(Figure
left-hand
side)
to interact
with
(Chapter
the
1.4.2).
The
six
ligand-orbital
combinations
2eg *
1e
t
s a1g
1u
ing
metal
orbitals
(Figure
2.2,
left-hand
side)
interact
withfor
de bonding
18 electrones
yof diamagn;cos
2eg
eg Compuestos
one the
must
analyse
the
orunderstand
antibonding
character
of
each
the
symmetry-adapted
combinations
orbitals
ontothe
six
ligands
at the
same
energy.
To
the
energetic
ordering
in Figu
1eg a1g
t
1u
si la done
iferencia
dcombinations
e energa
ntre
los
noriveles
y six
the
symmetry-adapted
of
orbitals
ligands
1t1u
2g the
(Figure
side).
must
analyse
the ebonding
antibonding
ischaracter
the
mostof eac
the ligandligand
interactions
(Figure
2.1).
The
a1gontorbital
a1g 2.2, right-hand
eenergetic
ealllevada
1a1g
(Figure
2.2,
right-hand
side). adopted
1t1u
g es
the
ligandligand
interactions
2.1).
a1g orbital
Thesince
ordering
the(Figure
metal
orbitals
follows
the is the
orbitals,
there
stable,
the
interactions
are for
bonding.
In the
t1uThe
t
2g
eg
1aL1g
The
formetals:
the
orbitals
follows
the
energetic
L
d t
orbitals,
stable,
since
all adopted
the between
interactions
are
bonding.
In
the
t1u
usual
rule
for
theordering
d-block
transition
(d)
<that
(s)
<trans
(p)
t2g L
is an
antibonding
interaction
twometal
ligands
are
to
L
e2gg
3 LOM L L L
d t
M
M
L
usual
rule
for
the
d-block
transition
metals:
(d)
<
(s)
<
(p)
2g
L
1, Due
is 1.4.2).
antoantibonding
interaction
between
ligands
(Chapter
sixdistance
ligand-orbital
combinations
arethe
notthat
all are tra
L
L
Lother.
each
theThe
large
between
thesetwo
ligands,
orbit6 e-
L
L
L
L
L
M
L M L
(Chapter
1,

1.4.2).
The
six
ligand-orbital
combinations
are
not
all
eg
L the
each
other.
Due
thethe
large
distance
between
ligands,
at
same
To
understand
energetic
ordering
inthese
Figure
2.2,eg the
L
als
be energy.
considered
to
betopractically
nonbonding.
For
the two
1eg
L may
Ligandos
qTo
ue
favorecen
q
ue
se cordering
umpla
L et1u
g
at
the
same
energy.
understand
the
energetic
in
Figure
2.2,
1e
g
Figure 2.2. Interaction
diagram
( only) forat 1g
6 OM
als may
considered
tosame
be practically
one
must
analyse
thelbe
bonding
character
of each
for the tw
- or
orbitals
(which
necessarily
have
theantibonding
energy),
itnonbonding.
is easier
to For
con1u
la
r
egla
d
e
os
1
8
e

-
e

:
the
metal
an octahedral12
complex
ML
only)
one
must analyse
the
bonding
or antibonding
of
each
a1g (
Figure 1t
2.2.
diagram
for
1u 6InteractionDonador
orbitals
(which
necessarily
haveThe
theacharacter
same
energy),
itmost
isfor
easier to
isligands
the
the
ligandligand
interactions
(Figure
2.1).
sider
the
first:
the
four
interactions
between
the
closer
(cis)
1g orbital
orbitals are on the
left
and
the
1t
:
the
metal
an octahedral
complex
ML
1u
6

Buenos
dinteractions
onadores
bonding.
orbital
isthe
thecloser
most
the
ligandligand
interactions
2.1). The
athe
1a1g
1gbetween
sider
the
first:weakly
the(Figure
four
interactions
orbitals,
there ligand
stable,
since
all
the
are
In
t
symmetry-adapted
ligand
orbitals
on
the
right.
1u
orbitals
are
on
the
left
and
the
are
antibonding,
but
two
bonding
interactions
occur
between
1a
1g
*
orbitals,
there
since
all
interactions
are
bonding.
In
the tthat
2eare
aantibonding,
umenta
su but
ebetween
nerga
L
1u interactions
L orbitals onstable,
symmetry-adapted
ligand
thean
right.
g the
two
weakly
bonding
occur
bet
is
antibonding
interaction
two
ligands
are
trans
to
L
L
orbitals
are
therefore
antibonding,
the
trans
ligands.
Overall,
the
e
g
L
L
L
L
M
L M LL
is
an other.
antibonding
interaction
between
two eligands
thatareare
trans
toantibon
L
to Buenos
aceptores
(abetween
orbitals
therefore
theenergetic
trans
ligands.
Overall,
the
each
Due
to
the
large
distance
ligands,
the
orbitg these
LL
L
)
(bonding)
<
(t
)
(nonbondleading
the
ordering:
M
LL M L
1g
1u
L
L L
each other.t Due
large
distance
these) ligands,
the<orbitL
(bonding)
(te1ugor) (non
the
energetic
(a
e(antibonding).
s to the
etonlazante
y smust
e ordering:
ebetween
stabiliza
L
als
be g2g
considered
to be
practically
nonbonding.
For
two
1g that
L
)leading
One
remember
thethe
bonding
ing)may
< (e
als
may
be
considered
to
be
practically
nonbonding.
For
the
two
eg bond
Figure 2.2. Interaction diagram ( only) for
must remember
the
ing)necessarily
< (eg ) (antibonding).
orbitals (which
have the sameOne
energy),
it is easier that
to conFigure
2.2. Interaction
diagram
only) for
metal
an
octahedral
complex ML
6 : the(
orbitals (which necessarily have the same energy), it is easier to consider the first: the four interactions between the closer ligands (cis)
:
the
metal
an
octahedral
complex
ML
6
orbitals are on the left and the
s a1g

2eg

Coordinacin
octadrica, DOM

complex.

1.6.1. Simplified interaction diagram

La regla de los 18 electrones

a2"+e

a1 s
a1+e+e

We shall consider, for simplicity, a complex in which the metal is

surrounded by ! identical ligands, each with just a single orbital that
can take part in the metalligand interaction (a interaction, 1.5.1).
A simplified diagram for the interaction between the ! ligand orbitals
and the nine atomic orbitals on the metal (five d orbitals, one s orbital,
Fundamento de la and
regla
e los 1
8 electrones
three pdorbitals,
without
distinction) is given in Figure 1.8. In this
diagram, the metal orbitals are placed higher in energy than those on the
ligands, since the latter are more electronegative. The ! ligand orbitals
a1+e+a2
interact with ! metal orbitals, to form ! bonding MO and the associated
! antibonding MO. There are therefore (9 !) nonbonding orbitals that
remain on the metal.
a1

Otras geometras:

En general hay 9 OM enlazantes

o dbilmente an;enlazantes

e+ e
2a1+e+a2

antibonding
MO

2a1+e+a2
M

t2

ML5 D3h

a1 s
e + t2

5L

9
metal

a1+ t2

AO

(9 )
nonbonding
MO

t2
e

ligand
orbitals

a1+ t2
Figure 1.8. Simplified
a + t2 diagram for the
interaction of the1 atomic
orbitals on a metal
centre
! ligands
which surround
it (
M and theML


T

4L
interactions only).4 d

bonding
MO

OC

electrons in terms of a

OC
Fe

OC

CO
H

OC

(23.27)

ence electrons
valence electrons
ectrons

CO

Fe

Fe(0) = 8 electrons
3 terminal CO = 3 2 electrons
2 -CO = 2 1 electron per Fe
FeFe bond = 1 electron per Fe
H = 1/2 electron per Fe
1 charge = 1/2 electron per Fe
Total = 18 electrons per Fe

La regla de los 18 electrones

Worked example 23.1 18-Electron rule

Excepciones comunes a la regla de los dieciocho electrones

a zero oxidation state

umber (e.g. Cr, 6; Fe,
ed ligands donate the
ns:

ding mode), and termor Ph) or RO!;

OR)3 , R2 CCR2 (Z2 -

Confirm that the Cr centre in g6 -C6 H6 CrCO3 # obeys the

Complejos
18-electron rule, but Rh in CO2 Rhl-Cl2 RhCO
2 # does plano cuadrados:
a
+a
+e

2u 1g u
not.
Son ms estables con 16 electrones
p
a2u+eu

a1g+eg+b1g+b2g

3.22), Z4 -C4 R4 (cyclo23.25), m3 -Cl!, m3 -Br!,

other Z6 -arenes, e.g.

Buenos aceptores

CO
CO

M
Cl

OC
Rh
OC

3 CO contribute
( 2 6 electrons
a +e3 +b

Complejos con ligandos donadores

a1gTotal
+b1g+eu
18 electrons
Complejos con nmero de ligandos
ML4 D4h
4L
limitado por impedimento estrico
Rh(0) (group 9) contributes
1g

OC

1g

9 electrons
m-Cl contributes 3 electrons
3
4 (1 to 5
one Rh and 2 to the other Rh)
Sc
Ti
V
CO 2 CO contribute 2 ( 2 4 electrons
CO

Rh
Cl

Complejos con ligandos que no son:

Cr(0) (group 6) contributes 6 electrons

Buenos donadores
6
b2gZ
+eg-C
+a61gH
6 contributes 6 electrons

Cr

radical), RC (carbyne),

b1g

a1g s

Rh(0) 9 electrones

iscussion at the end of2 CO 2x2 electrones

exercises
-Cl Self-study
3 electrones

1. Confirm
that the
TOTAL
16 electrones
5
$

Y
Zr
Total per Rh 16 electrons

por tomo
de Rh

La

Hf

10

11

Cr

Mn

Fe

Co

Ni

Cu

Nb

Mo

Tc

Ru

Rh

Pd

Ag

Ta

Re

Os

Ir

Pt

Au

Fe centres in H2 FeCO4 and

Al principio y al nal de las series las
g -C5 H5 FeCO2 # obey the 18-electron rule.
excepciones son ms comunes
2. Show that FeCO4 g2 -C2 H4 , HMnCO3 PPh3 2 and
g6 -C6 H5 BrMnCO3 # contain 18-electron metal centres.

2 is as
assigned
the metal:
Fe(II)avoids
(6 valence
electrons)
formally represented by structure 23.26, i.e. one electron is
ligands
neutralto entities
as this
the need
to
$

CO
donor).
inone
this donated to M,O
and two
Cp ligands
a doubly
bridged species
assign
an oxidation
state(6-electron
to the metal
centre.
However,
= 8 electrons
BlackHowever,
plate (708,1)
C and two to M. InFe(0)
OC
book
shall
always
count
in termsFor
of a such as CO2 Rhm-Cl2CO
RhCO2 , 3the
m-Cl atoms
must
notwelose
sight
of the
fact valence
that thiselectrons
is a formalism.
2 equivaelectrons
terminal
CO = 3are
OC
Fe
zero oxidation
state metal
=2
1 electron
per Fe
lent as are the Rh atoms, and the2 -CO
two Cl
bridges
together
example,
in the synthesis
of centre.
cyclopentadienyl derivatives, a
Fe

$
!
FeFe
bond
=
1
electron
per Fe
contribute
three electrons to each Rh. A bridging H provides
common precursor is the salt Na Cp# . Ferrocene, Cp2 Fe,
OC
CO
1/ electron per Fe
ompounds of d-block
elements
H
=
2 the metal atoms it
may be formulated as an Fe(II) compound containing
only one electron
in total, shared between
H
OC
Electron count:
$
$
1
charge
= 1/2 electron
peralso
Fe
23.27
[Cp] ligands, but for electron counting, it is convenient to
bridges, e.g. in HFe2 CO8 # , (23.27). Example
Total = 18 electrons per Fe
(23.27)
consider Counting
the combination
ofprovided
an= Fe(0)
centre
(group 8, 8
illustrates that the formation of an M$M single bond provides
tals from the middle
by! bridging
8 valence
electronsligands, metalmetal
Fe electronsFe(0)
valence electrons)
ligands
(5-electron
each M atom with one extra electron; an MM double bond
= 2Cp
5 valence
electrons
2 neutral
Cp requires
e and its application
bonds andand
net two
charges
care.
When
bridging between
an 18-electron
(23.25).
two electrons to each metal.
18
electrons
uses
posed structures.donor)
For giving
two metal
centres,Total
an complex
X=! (X
Cl,
Br, I)Of
or course,
R2 P! ligandcontributes
Worked example 23.1 18-Electron rule
the
same
result
is
obtained
if
a
formal
oxidation
state
of
Electron count:
the unpaired electron and one lone pair to give an interaction
venient to treat all
2
is
assigned
to
the
metal:
Fe(II)
(6
valence
electrons)
6
formally
represented(23.25)
by structure 23.26, i.e. one electronConfirm
is
avoids the need to
that
Cr centre
$
in g -C6 H6 CrCO3 # obeys the
O theCO
ligands
(6-electron
donor).
However,
in
this
and
two
Cp
Fe(0) = 8 electrons
C rule, but Rh in CO
donated to M, and two to M. In a doubly bridged species
centre. However, one
OC
18-electron
2 Rhl-Cl2 RhCO2 # does
book
we
shall
always
count
valence
electrons
in
terms
of
a
3eutro
terminal CO = 3 2 electrons
Cuenta
e
lectrnica:
e
mpleamos
e
l
f
ormalismo
n
The number
valence
electrons
for
a
zero
oxidation
state
CO
Rhm-Cl
RhCO
,
the
m-Cl
atoms
are
equivasuch asofCO
s is a formalism. For
2
2
2
not.
OC
Fe
zero
metal
centre.
2 -CO = 2 1 electron per Fe
metal
centre
isare
equal
the
groupand
number
(e.g.ClCr,
6; Fe,together
lent asstate
the to
Rh
atoms,
the two
bridges
adienyl derivatives,
a oxidation
Fe

FeFe bond = 1 electron per Fe

$
!
OC
donateHtheprovides
8; Rh, 9);
some commonly
encountered
ligands
. Ferrocene, Cp Fe,
contribute
three electrons
to each Rh.
A bridging

La regla de los 18 electrones

CO

26 electrones
Ferroceno
Cr(0)

following
numbers
of valence
electrons:
Cr(0)
(group
6) contributes
6 electrons
ompound containing
only
one electron
in total,
shared
between the metal atoms it OC
H
Electron
count:
1 charge = 1/2 electron per Fe
$
6
6
g, it is convenient to
CO8 # , (23.27). Example 23.27 also
bridges, e.g. in HFe
Z -C
H66H
contributes
6electrons
electrons
6-C
6= e18lectrones
! (in 2any
Total
per Fe
6
(23.27)
Fe(0)
bonding

8M$M
emode),
lectrones
donor:
H
andbond
term-provides
) centre (group 8,. 8 1-electron
illustrates
that
the
formation
of
an
single
Fe(0) 5= 8 valence electrons
Cr
Fe ! !
!
!
!
3
CO
contribute
3
(
2

6
electrons
3 CO 3x2 electrones
Cl , Br
I , Rwith
(e.g.
alkyl
or
Ph) e
orlectrones
RO ; double bond
R
one
-Cp
2x5
p! ligands (5-electron inal each
M ,atom
electron;
an
MM
= extra
2 5
valence
electrons
22
Cp
2
OC
CO
. 2-electron donor: CO,
PR
, electrons
P(OR)3 , R2 CCR2 (Z = 318
Total TOTAL
18 electrons
(23.25). Of course,
contributes two Total
electrons
to each metal.
1rule
8 electrones
Worked
example
23.1 18-Electron
CO
TOTAL
1
8
e
lectrones
alkene), R2 C: (carbene);
al oxidation state of
ElectronRC
count:
(carbyne),
. 3-electron donor: Z3 -C3 H5 ! (allyl radical),
6
6 valence electrons)
(23.25)
9) contributes
!
!
!
!
Confirm that the Cr centreRh(0)
in g(group
-C6 H6 CrCO
3 # obeys the
m-Cl , m-Br , m-IO, m-RCO
P;

2
or). However, in this
9
electrons
Fe(0)
=
8
electrons
4
4
Rhl-Cl
RhCO
18-electron
rule,
but
Rh
in
CO
C
2
2
2 # does
. 4-electronOCdonor: Z -diene (e.g. 23.22), Z -C4 R4 (cycloCl
OC
CO
ectrons in terms The
of anumber of valence electrons
for
a
zero
oxidation
state
=
3

2
electrons
3
terminal
CO
CO
m-Cl contributes 3 electrons (1 to
not.
butadienes);
metal centreOC
is equal to Fe
number
(e.g.= 2Cr,
Fe,
2 -CO
1! 6;
electron
per
Fe
Rh
Rh
5the group
one Rh and 2 to the other Rh)
!
!
. 5-electron donor:
Z -C5 H5 (as in 23.25),
, electron
m-3 -Br ,per Fe
m3 -ClH]
Fe
[
Fe
(CO)
FeFe
bond
=
1
donate
the
8; Rh, 9);! some
commonly
encountered
ligands
2
8
!
OC
Cl
CO 2 CO contribute 2 ( 2 4 electrons
CO
m3 -I , mOC
1
3 -RP ;
per Fe
following
numbers
of valence
electrons: H = /2 electron
Cr(0) (group 6) contributes 6 electrons
6
6
H
. 6-electron OC
donor: Z -C6 H6 (and other
Z -arenes,
e.g.per Fe
1 charge
= 1/2 electron
per Rh 16 electrons
6
Z6 -C6 HTotal
6 contributes 6 electrons
!
-C
H
Me);
Z
6 5 donor:(23.27)
= and
18 electrons
. 1-electron
H (in any bonding Total
mode),
term- per Fe
8(e.g.
electrones
Cr
!,3-electron
!; end of
3 CO contribute 3 ( 2 6 electrons
ce electrons
.inal
1- Cl
orFe(0)
(see discussion
at the
Br!, I!, R!donor:
RNO
alkyl
or Ph) or RO
Self-studyCO
exercises
alence electrons
2
Section 20.4).
OC
. 2-electron
donor:
3 , P(OR)3 , R2 CCR2 (Z Ni(0) Total
10 e
lectrones
4 CO
4CO,
x2 ePR
lectrones
18 electrons
trons
CO
example 23.1 18-Electron rule
alkene),Worked
R2 C: (carbene);
1. Confirm
that the Fe centres in H2 FeCO4 and

H electrn
por
tomo
(allyl radical), RC
(carbyne),
. 3-electron donor: Z3 -C3 H5 ! X
g5 -C5 H5 FeCO2 #$ obey the 18-electron rule.
6
(group 9) contributes
!, m-R
!; centre M'
de Fe 3 # obeys the5-Cp 5 eRh(0)
lectrones
- ! , m-I

the
e2Mlectrn
that
in g -C6 H6 CrCO
por tomo
m-Cl!, Confirm
m-Br
PCr
2
g -C2 H4 , HMnCO3 PPh3 2 and
2. Show that FeCO94 electrons
4
4
Rhl-Cl
RhCO
#
does
18-electron
rule,
but
Rh
in
CO
. 4-electron
donor:
(e.g. 23.22), 2Z -C4 R4 (cyclo(23.26)

2
2 OC -PPh
de
Ni centres.
CO
3 em-Cl
lectrones
Fe-Fe
Z1 -diene
electrn
g6 -CCl6 H25 BrMnCO
contain 18-electron
metal
3 # contributes
zero oxidation state
3 electrons
(1 to
not.
butadienes);

Rh
Rh
mber (e.g. Cr, 6;. Fe,
one
Rh and 2 to the other Rh)
! (as in 23.25), m -Cl!, m -Br!,
3. Show
that RhPMe
TOTAL
18 electrones
3 4 # contains a 16-electron metal centre.
TOTAL
e5lectrones
5-electron donor:
Z51
-C8
5H
3
3
d ligands donate the
!
!
Comment
on
whether
violation
of the
rule is
2 (18-electron
2 4 electrons
OC
Cl
CO 2 CO contribute
m3 -I , m3 -RP ;
:
(group
6) contributes
electrons expected.
. 6-electron donor: Z6 -C6Cr(0)
H6 (and
other
Z6 -arenes, 6e.g.
6
Total per Rh 16 electrons
6
Notation
bridging ligands:Zsee
6.7.
-CSection
Me);
Z -C6 H5for
6 H6 contributes 6 electrons
ng mode), and term-

H = 1/ electron per Fe