5.

111 Lecture Summary #29 Friday, November 21, 2014

Reading For Today: 16.8-16.11 in 4th and 5th editions

Reading for Lecture #30: 14.1-14.5 in 5th ed and 13.1-13.5 in 4th ed.

Topic: I. Spectroscopic Theory: Both Ligand Type and Geometry Make a Difference
II. Crystal Field Theory: Tetrahedral Case
III. Crystal Field Theory: Square Planar Case
IV. Other Geometries and Applications
I. Spectroscopic Theory: Both Ligand Type and Geometry Make a Difference
Nickel Demonstration
Recall the color of light transmitted is complementary to the color of light that is
absorbed. Red is complementary to green; orange is complementary to blue; yellow is
complementary to violet.

[NiCl6]4- (greenish)
Absorbs λ that is ___________; so !o is ;Cl - is a field ligand
H2O
[Ni(H2O)6]2+ (blue-green)
Absorbs λ that is ________________than above; so !o is than above;
H2O is a fiel d ligand than above
EDTA
Ni-EDTA (blue)
Absorbs λ that is ________________than above; so !o is than above;
EDTA is a field ligand than above

Also [Ni(H2O)6]2+ (blue-green)

dimethylglyoxine (dmgH)
Ni-(dmgH)2 (red)
Absorbs λ that is ________________than above; so ! is ___________________; but the
complex is square planar and not octahedral. Geometry matters. Square planar
geometry must allow for a large splitting of the energy of the d-orbitals.
(We will look at this in a few minutes.)

violet blue green yellow orange red

| | | | | | |
λ 400nm 430nm 490nm 560nm 580nm 620nm 800nm

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II. Crystal Field Theory: Tetrahedral Case

z axis
Z
L- L- Z

M y axis Y Y
X
L- X
L-
x-axis out of the page dx2-y2 dz2

tetrahedral

z axis
L- L- Z
Z
Z

M y axis Y Y Y
X X
L- L- X
dyz dxy
x-axis out of the page dxz

tetrahedral

• There is ___________repulsion between the ligand negative point charges and the
d-orbitals that are 45° off axis (dyz, dxz, dxy) than there is between the ligand negative
point charges and the d-orbitals that are on axis (dz2 and dx2-y2).

• As a result of the above, there is greater orbital destabilization for dyz, dxz, dxy than
for dx2-y2 and dz2 ( of octahedral).

• dz2 and dx2-y2 have the energy with respect to each other (degenerate).

• dyz, dxz, dxy have the same energy with respect to each other (degenerate).

• The tetrahedral crystal field splitting energy (∆T) is than for

octahedral complexes because the point charges are not directed at any orbital set.

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 (eg)
E dx2-y2 dz2
+3 (t2) + 2
O dxy dxz dyz
5 T
O 5
-2 T
- 3 T
O
average energy of 5 dx2-y2 dz2 (e) 5
d orbitals with ligands dxy dxz dyz (t2g)
(Spherical crystal field) (Octahedral crystal field) (Tetrahedral crystal field)

 ∆o and ∆T are the octahedral and tetrahedral crystal field splitting energy, respectively
 Again, the positioning of the orbitals is opposite for tetrahedral and octahedral
 dxy, dxz, and dyz orbitals are now called t2 and dx2-y2 and dz2 are e
 ∆T is ________________ than ∆o because the point charges are not directed at any
orbital set in a tetrahedral crystal field.
 Because ∆T is small, many tetrahedral complexes are .
 You can assume that they are all high spin!
 Because the overall energy in the tetrahedral crystal field is maintained, t2 orbitals
go up in energy by 2/5, and the e orbitals go down in energy by 3/5.

Tetrahedral Example for Cr3+

(a) figure out d electron count

(b) draw tetrahedral crystal field splitting diagram, label orbitals, and fill in electrons

E
(t2)

average energy of (e)

d orbitals with ligands

(Spherical crystal field) (Tetrahedral crystal field)

(c) Write dn electron configuration:

(d) How many unpaired electrons?

(e) If this compound is [CrCl6]3- and the wavelength of most intensely absorbed light is 740
nm, predict the color of the complex.

3
III. Crystal Field Theory: Square Planar Case
Z-axis Z
Z

L-

L- Mn+ L- Y-axis Y Y

X
X
L- dx2-y2 dz2

X-axis

Square planar repulsion much less repulsion than

ligand point charges in octahedral crystal field.
directed at orbitals Less repulsion than
Destablized compared for dx2-y2 and for dxy
to all other d-orbitals
Z
Z
Z-axis Z
L-

L- Mn+ L- Y-axis Y Y Y
X X
L- X
X-axis dyz dxy
dxz
Square planar stabilized compared stabilized compared repul sion than for dxz,
to dxy and dx -y
2 2
to dxy and dx -y
2 2
dxz, and dz2. Less repulsion
than for dx2-y2 since orbitals
are 45° off axis in dxy.
Z
The overall
Y energy of
X the square
dx2-y2

planar
(eg) Z crystal field
E is also
dx2-y2 dz2 Y
+3/5 O X maintained,
but the
dxy

O
Z relative
-2/5 O energies of
average energy of
d orbitals with ligands (t2g) Y each of the
dxy dxz dyz X d-orbitals
(Spherical crystal field) (Octahedral crystal field) dz2 are more
(square planar
complicate
L- Z
L- crystal field) Z d and you
L-
Y Y
are not
L- M n+ L- X X expected to
L- M n+ L- dyz
dxz know them.
L- L-
L-

4
IV. Other Geometries Z-axis Z-axis

-L
L- L-
What about square
pyramidal? L- Mn+ L- Y-axis L- Mn+ L- Y-axis

L- L-

X-axis X-axis

square planar square pyramidal

dz2 is for square pyram idal compared to square planar

dxz and dyz are for square pyram idal compared to square planar
d x2- y2 and dxz are degenerate f or square pyramidal

And Applications to metalloenzymes (Nickel enzyme example)

Nickel dependent enzymes are responsible for removing ~100 million tons of CO from the
atmosphere each year and producing ~1 trillion kg of acetate from greenhouse gases and
other carbon sources. We want to know what these nickel-based catalysts look like, so that
we can mimic this chemistry.

To probe the geometry of the nickel cofactor, spectroscopy was used and it was found that
the Ni2+ (d8) center was diamagnetic. Predict whether it has square planar, tetrahedral, or
octahedral geometry?
dx2-y2

E dx2-y2 dz2
dxy dxy dxz dyz

dx2-y2 dz2
dz2
dxy dxz dyz

(Octahedral dxz dyz (Tetrahedral crystal field)

crystal field)
(Square planar
crystal field)
Answer:
The Ni center in the enzyme must be .

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5.111 Principles of Chemical Science

Fall 2014

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