Outline

Molecular Orbitals in Metallic dimers

Ligand symmetry adapted orbitals and
Inorganic Chemistry the isolobal analogy
The octahedral point group
Dr. P. Hunt
p.hunt@imperial.ac.uk
Rm 167 (Chemistry) next lecture combine all this information
to form the MO diagram for a
http://www.ch.ic.ac.uk/hunt/ TM Octahedral complex!

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Octahedral Complexes Octahedral Complexes

transition metal surrounded by six - z
Fig. 1 know how to draw dAOs!
donor ligands L in an octahedral geometry L positive lobe in quadrant defining the orbital
L L
MO diagram describes the interaction y L M
L x z z

between the metal AOs and ligand FOs L dz2

Metal orbitals x
4p t1u x
dx2-y2
different from main group metals spherical y
y
include the 3d (or 4d) AOs
AND the 4s and 4p (or 5s and 5p) unoccupied AOs positive in xz
4s a1g quadrant z z z side on dAO
AO symmetry octahedral dxz dyz
assume Oh symmetry (initally!)
use short-cuts! 3d eg t 2 g x x
dxy
x
dAOs use binary functions y y y
pAOs use Tx, Ty, Tz Fig. 2
Fig. 3
sAO is totally symmetric
Metal FOs

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 metal so include

Metallic Dimers the unoccupied s and p

orbitals in MO diagram
Symmetry Tip
p -> g g +,

M2 homonuclear diatomic classify interactions

Energy diagram -type

has energy levels symmetric for
only include key MOs rotation about z-axis
s -> g+

Dh point group -type

single phase
symmetry lables from dAO-dAO splitting Important!
read FO symmetry off the Dh character table (using short cuts) is very small change on rotation
about z-axis
character table
s-> g+ -type
d -> g+, g, g
pz-> u+ px & py-> u two phase changes on
dz2-> g+ x rotation about z-axis
expand
dxy, dx2-y2-> g z Fig. 6
M M
dyz, dxz -> g
y
M M M M
homonuclear diatomic
z-axis is the principle axis and lies along the bond
Fig. 4

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Metallic Dimers Metallic Dimers

focus dAO region complete the MO symmetry
combine FO bonding and labels
antibonding pairs
dz2-> (green) focus on phase
dxy, dx2-y2-> (pink) change around looks like z-axis -> u+
center of
dyz, dxz -> (blue)
inversion also

along the bond ->

inverts through i -> u
dxy dx2-y2
-type no phase change for v -> +
dxy
-type
dx2-y2
symmetric for
rotation about z-axis
-type dyz dxz
-type x
single phase dyz dxz
change on rotation
about z-axis z -type dz2 x
M M

-type y dz2
M M z
two phase changes on
rotation about z-axis
M M M M y
Fig. 6
Fig. 5 Fig. 7

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Metallic Dimers Metallic Dimers
complete the MO symmetry complete the MO symmetry
labels labels
focus on phase focus on phase
change around change around no dAO analogy
looks like dxz & dyz -> g
center of center of
inversion inversion but
also
around bond
around bond inverts through i -> u
symmetric through i -> g dxy dx2-y2 must be u dxy dx2-y2
no +/- label for

dyz dxz dyz dxz

dz2 x dz2 x

M M z M M z
y y
Fig. 7 Fig. 7

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Metallic Dimers Metallic Dimers

complete the MO symmetry complete the MO symmetry
labels labels
focus on phase focus on phase
change around change around
center of center of
inversion inversion

looks like dxz & dyz -> g dxy dx2-y2 dxy dx2-y2
looks like px & py -> u
also
dyz dxz also dyz dxz
around bond
symmetric through i -> g around bond
dz2 x dz2 x
inverts through i -> u
M M z no +/- label for M M z
y y
Fig. 7 Fig. 7

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 Metallic Dimers Metallic Dimers
complete the MO symmetry bond order
labels ONLY applies to diatomics
u+

fill 5 bonding dAOs

focus on phase
change around quintiple bond! u
center of
inversion
configuration: 244
d -> g+, g, g u
R
dxy dx2-y2
R
R R g
Cr Cr
dxy dx2-y2
looks like sAO -> g +
dyz dxz
R
R
R
x
u
also dyz
dz2 x R M M z dxz
Fig. 7b
along the bond -> z Power: 2005
y
g+
symmetric through i -> g M M dz2
y link to paper on
no phase change for v -> + web-site
Fig. 7 Fig. 7a M M M M Fig. 8

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Ligand Fragment Orbitals Ligand Fragment Orbitals

symmetry can be used to Symmetry Adapted symmetry can be used to Symmetry Adapted
determine the ligand FOs orbitals determine the ligand FOs orbitals
not covered this year, but notes not covered this year, but notes
are available on-line if you are are available on-line if you are
interested interested

SA orbitals are general SA orbitals are general

you should know these for L2, L3, you should know these for L2, L3,
L4, L5, L6 L4, L5, L6
can also be used to predict some
of the pAO combinations
H 1s AO

symmetry adapted symmetry adapted

sAOs p zAOs

L L2 L3 L4 L5 L6
Fig. 9 Fig. 10

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 Ligand Fragment Orbitals Octahedral SA Orbitals
symmetry can be used to symmetry can be used to
Symmetry Adapted
determine the ligand FOs
6 = A1g + Eg + T1u
determine the ligand FOs orbitals
not covered this year, but notes use tricks to remember the
are available on-line if you are phase patterns
same phase as
interested
degenerate dx2-y2 and dz2
SA orbitals are general eg axial
you should know these for L2, L3, symmetry t1u
+
L4, L5, L6
can also be used to predict some eg
of the pAO combinations
degenerate orbitals can rotate
+ t1u
among themselves

equivalent set a1g

of degenerate
orbitals
totally
Fig. 11
Fig. 10
symmetric a1g

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Isolobal Analogy Ligand Fragment Orbitals

Ligand fragment orbitals Fig. 12

eg

only some orbitals are important

1b2
t1u
key orbital has like characteristics VERY
these mimic the 1sAO orbital of H 3a1 Important!
a1g
looking from the metal orbital appears as sAO
isolobal to sAOs
Fig. 11
typically the HOMO of the ligand HOMO HOMO-1
BUT not always, can be a deeper MO of NH3 of H2O

eg
-type ligands:
all have -type FOs which interact with the TM t1u
NH3, NR3, PH3, PR3, OH2, R-, CR3, SiR3
a1g

Fig. 13

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