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PROFESSOR: OK, let's just
take 10 more seconds on

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the clicker question.
 

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OK, 76, I think that says,
%, which is not bad, but

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we should be at 100%.
 

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So, when you're past the
equivalence point, so you've

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converted all of your weak, in
this case, acid to its

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conjugate base, and because it
was a weak acid, the conjugate

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base is going to be a weak
based and so it's not

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contributing a whole lot it'll
make the solution basic, but

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it's nothing compared to adding
strong base in there.

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So even though you have
the weak base around, at

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this point it's really
a strong base problem.

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So you would calculate this by
looking at how many mils of the

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strong base you've added past,
and figure out the number of

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moles that there are, and
divide by the total volume.

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So this was like one of the
problems on the exam, and one

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thing that I thought was
interesting on the exam is that

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more people seemed to get the
hard problem right than this,

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which was the easy problem.
 

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So we'll see on the final,
there will be an acid based

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titration problem on the
final, at least one.

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So let's see if we can
get, then, the easy and

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the hard ones right.
 

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So you've mastered the hard
ones and let's see if you can

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learn how to do the easy ones
as well for the final exam.

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OK, so we're going to continue
with transition metals.

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We were talking about crystal
field theory and magnetism, and

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you should have a handout for
today, and you should also have

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some equipment to make models
of orbitals and coordination

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complexes -- these
are not snacks.

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They can be snacks later, right
now they're a model kit.

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All right, so I'm going to
introduce you to some terms

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that we're going to come back
you at the end of today's

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lecture, and then we're going
to talk about the shapes of

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coordination complexes.
 

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So, magnetism.
 

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So we talked last time, before
the exam, if you remember,

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about high spin and low spin,
unpaired electrons and

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paired electrons.
 

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Well, compounds that have
unpaired electrons are

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paramagnetic, they're attracted
by a magnetic field, and those

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where the electrons are paired
are diamagnetic are repelled

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by a magnetic field.
 

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So you can tell whether a
coordination complex is

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paramagnetic or diamagnetic,
you can test the magnetism,

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and that'll give you some
information about the electron

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configuration of the d orbitals
in that coordination complex.

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And that can tell you
about the geometry.

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And so you'll see that by the
end we're going to talk about

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different types of energy
orbitals when you have

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different geometries.
 

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So why might you care about the
geometry of a metal center.

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Well, people who study proteins
that have metal centers care a

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lot about the geometry of them.
 

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So let me just give
you one example.

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We talked a lot about energy in
the course this semester, so we

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need catalysts for removing
carbon monoxide and carbon

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dioxide from the environment.
 

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And nature has some of these --
they have metal cofactors and

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proteins that can do this, and
people have been interested in

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mimicking that chemistry
to remove these gases

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from the environment.
 

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So let me tell you these
enzymes are organisms.

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And this is pretty amazing,
some of these microorganisms.

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So, over here there's one
-- it basically lives

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on carbon monoxide.
 

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I mean that's -- you know
alternative sources of energy

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are one thing, but that's
really quite a crazy thing

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that this guy does.
 

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So, you can grow it up in these
big vats and pump in carbon

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monoxide and it's like oh,
food, and they grow and

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multiply, and they're very,
very happy in this carbon

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monoxide environment.
 

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There are also microorganisms
that live on carbon dioxide as

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their energy and
a carbon source.

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And so these organisms have
enzymes in them that have metal

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centers, and those metal
centers are responsible for the

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ability of these organisms to
live on these kind of bizarre

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greenhouse gases
and pollutants.

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So people would like to
understand how this works.

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So microbes have been estimated
to remove hundred, a million

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tons of carbon monoxide from
the environment every year,

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producing about one trillion
kilograms of acetate from

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these greenhouse gases.
 

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And so, what do these catalysts
look like and these enzymes,

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what do these metal clusters
look like that do

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this chemistry.
 

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And this was sort of a rough
model of what they look like,

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and they thought it had iron
and sulfur and then a nickel in

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some geometry, but they had no
idea sort of where the nickel

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was and how it was coordinated.
 

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And so before there was any
kind of three dimensional

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information, they used
spectroscopy, and they

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considered whether it was
paramagnetic or diamagnetic to

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get a sense of what the
geometry around the metal was.

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So we're going to talk about
different coordination

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geometries and how many
unpaired or paired electrons

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you would expect, depending
on those geometries today.

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And so, crystal field theory,
again, can help you help

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explain/rationalize the
properties of these transition

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metal complexes or
coordination complexes.

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So, to help us think about
geometry, I always find

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for myself that it's
helpful to have models.

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So not everyone can have such
large models as these, but you

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can all have your own little
models of these geometries.

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So, what we have available to
you are some mini marshmallows,

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which, of course, as we all
know, are representative of d

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orbitals, and jelly beans,
which we all know are useful

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for making coordination
complexes.

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So, what you can do with your
mini marshmallows is you can

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put together to make
your different sets.

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And so, over here we have --
oh, actually it says gum drops

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-- you don't have gum drops
this year, I changed up here, I

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forgot to change it down here.
 

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We have mini marshmallows.
 

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Dr. Taylor went out and tried
to purchase enough gum drops to

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do this experiment, and
discovered that Cambridge only

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had 300 gum drops, so we have
mini marshmallows

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instead today.
 

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But this gives you the idea.
 

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You can take one toothpick and
you can make d z squared,

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putting on your orbitals, you
have your donut in the middle,

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and then your two lobes,
which run along the z-axis.

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And then for your other sets of
orbitals, you can take these

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two toothpicks and put on these
sets of mini marshmallows, and

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handily, you can just have one
for all of the other d

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orbitals, because depending on
how you hold it, it can

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represent all of the other d
orbitals just very well.

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So, you can just have one of
these for all the others

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and then your d z squared.
 

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So what we're going to do when
we have our orbitals set up,

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then we can think about how
ligands in particular

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positions, in particular
geometries would clash with our

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orbitals -- where there'd be
big repulsions or

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small repulsions.
 

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So, any other people missing
their jelly beans or

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their marshmallows?
 

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Please, raise your
hand, we have extras.

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So, those of you who have
them, go ahead and start

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making your d orbitals.
 

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00:10:08 --> 00:10:54
All right, so if you're
finished with your two d

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00:10:54 --> 00:11:01
orbitals, you can start making
an octahedral complex.

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00:11:01 --> 00:11:05
So in your geometries set,
you'll have a big gum which can

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be your center metal -- you'll
have a big jelly bean -- sorry,

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big jelly beans and small jelly
beans are our ligands, or our

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negative point charges, and
you can set up and make an

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octahedral geometry here.
 

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OK, so as you're finishing this
up, I'm going to review what we

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talked about before the exam --
so this isn't in today's

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lecture handouts, it was in
last time, which we

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00:13:15 --> 00:13:17
already went over.
 

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But sometimes I've discovered
that when there's an exam in

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the middle, there needs to be a
bit of a refresher, it's hard

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to remember what happened
before the exam, and you

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have your models to
think about this.

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So, before the exam, we had
talked about the octahedral

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case, and how compared to a
spherical situation where the

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ligands are everywhere
distributed around the metals

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where all d orbitals would be
affected/repulsed by the

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ligands in a symmetric fashion
equally, when you have them put

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as particular positions in
geometry, then they're going to

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affect the different d
orbitals differently.

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And so, if you have your d z
squared made, and you have your

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octahedral made, you can sort
of hold these up and realize

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that you would have repulsion
from your ligands along the

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z-axis directly toward your
orbitals from d z squared.

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So that would be
highly repulsive.

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00:14:16 --> 00:14:20
The ligands are along the
z-axis, the d orbitals are

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along the z-axis, so the
ligands, the negative point

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charge ligands are going
to be pointing right

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toward your orbitals.
 

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And if you hold up this as a d
x squared y squared orbital

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where the orbitals are right
along the x-axis and right

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00:14:38 --> 00:14:41
along the y-axis and you hold
that up, remember, your ligands

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are right along the x-axis
and right along the y-axis.

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00:14:45 --> 00:14:49
So, you should also have
significant repulsion for d x

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00:14:49 --> 00:14:53
squared minus y squared, and
octahedrally oriented ligands.

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In contrast, the ligands set
that are 45 degrees off-axis,

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00:15:01 --> 00:15:08
so d y z, d x z, and d x y,
they're all 45 degrees off.

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00:15:08 --> 00:15:11
Your ligands are along the
axis, but your orbitals

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are 45 degrees off-axis.
 

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00:15:14 --> 00:15:16
So if you look at that
together, you'll see that

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00:15:16 --> 00:15:19
whichever one you look at, the
ligands are not going to be

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00:15:19 --> 00:15:22
pointing directly toward
those d orbitals.

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00:15:22 --> 00:15:24
The orbitals are off-axis,
ligands are on-axis.

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So there will be much
smaller repulsions there.

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And that we talked about the
fact that for d x squared minus

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y squared and d z squared,
they're both have experienced

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large repulsions, they're both
degenerate in energy, they go

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up in energy, whereas these
three d orbitals, smaller

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repulsion, and they're also
degenerate with respect to each

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other, and they're stabilized
compared to these guys up here.

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So you can try to hold those up
and convince yourself that

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that's true for the
octahedral case.

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00:16:01 --> 00:16:04
So, that's what we talked about
last time, and now we want to

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00:16:04 --> 00:16:08
-- oh, and I'll just remind you
we looked at these splitting

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00:16:08 --> 00:16:09
diagrams as well.
 

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We looked at the average energy
of the d orbitals -- d z

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00:16:13 --> 00:16:17
squared and d x squared minus
y squared go up in energy,

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00:16:17 --> 00:16:24
and then the other three d
orbitals go down in energy.

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00:16:24 --> 00:16:27
So now we want to consider
what happens with

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different geometries.
 

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00:16:31 --> 00:16:35
So now you can turn your
octahedral case into a

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00:16:35 --> 00:16:42
square planar case, and
how am I going to do that?

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00:16:42 --> 00:16:45
Yeah, so we can just take off
the top and the bottom and we

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00:16:45 --> 00:16:51
have our nice square planar
case, and try to make a

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00:16:51 --> 00:16:57
tetrahedral complex as well.
 

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00:16:57 --> 00:16:59
And here's an example
of a tetrahedral one.

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00:16:59 --> 00:17:02
Again, you can take a jelly
bean in the middle, and big

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00:17:02 --> 00:17:05
jelly bean, and then the
smaller ones on the outside.

219
00:17:05 --> 00:17:08
So what angles am I going for
here in the tetrahedral case?

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00:17:08 --> 00:17:10
109 .
 

221
00:17:10 --> 00:17:11
5.
 

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00:17:11 --> 00:17:15
So you can go ahead and make
your tetrahedral complex,

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00:17:15 --> 00:17:17
and don't worry so
much about the 0 .

224
00:17:17 --> 00:18:36
5, but we'll see if people can
do a good job with the 109.

225
00:18:36 --> 00:18:40
OK, how are your tetrahedral
complexes coming?

226
00:18:40 --> 00:18:46
Do they look like this sort of?
 

227
00:18:46 --> 00:18:49
So let me define for you how
we're going to consider

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00:18:49 --> 00:18:52
the tetrahedral case.
 

229
00:18:52 --> 00:18:56
So, in the tetrahedral case,
we're going to have the x-axis

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00:18:56 --> 00:19:00
comes out of the plane, the
y-axis is this way, z-axis

231
00:19:00 --> 00:19:02
again, up and down.
 

232
00:19:02 --> 00:19:05
We're going to have one ligand
coming out here, another going

233
00:19:05 --> 00:19:07
back, and then these two
are pretty much in the

234
00:19:07 --> 00:19:09
plane of the screen.
 

235
00:19:09 --> 00:19:12
So this is sort of how I'm
holding the tetrahedral complex

236
00:19:12 --> 00:19:18
with respect to the x, z,
and y coordinate system.

237
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So, there is a splitting,
energy splitting, associated

238
00:19:21 --> 00:19:25
with tetrahedral, and it's
going to be smaller than

239
00:19:25 --> 00:19:29
octahedral because none of
these ligands will be pointing

240
00:19:29 --> 00:19:31
directly toward the orbitals.
 

241
00:19:31 --> 00:19:36
But let's consider which
orbitals are going to be most

242
00:19:36 --> 00:19:42
affected by a tetrahedral case.
 

243
00:19:42 --> 00:19:48
So, let's consider d z squared.
 

244
00:19:48 --> 00:19:49
What do you think?
 

245
00:19:49 --> 00:19:52
Is that going to be
particularly -- are the ligands

246
00:19:52 --> 00:19:55
pointing toward d z squared?
 

247
00:19:55 --> 00:19:57
No.
 

248
00:19:57 --> 00:20:01
And d x squared minus y
squared, we can think of,

249
00:20:01 --> 00:20:04
what about that one?
 

250
00:20:04 --> 00:20:06
No, not really.
 

251
00:20:06 --> 00:20:12
What about d x y,
d y z, and d x y?

252
00:20:12 --> 00:20:17
Moreso.
 

253
00:20:17 --> 00:20:20
So, if you try holding up your
tetrahedral in our coordinate

254
00:20:20 --> 00:20:25
system, and then hold your d
orbitals 45 degrees off-axis,

255
00:20:25 --> 00:20:28
it's not perfect, they're not
pointing directly toward them,

256
00:20:28 --> 00:20:31
but it's a little closer than
for the d orbitals that

257
00:20:31 --> 00:20:36
are directly on-axis.
 

258
00:20:36 --> 00:20:41
So, if we look at this, we see
that the orbitals are going to

259
00:20:41 --> 00:20:46
be split in the exact opposite
way of the octahedral system.

260
00:20:46 --> 00:20:50
In the octahedral system, the
ligands are on-axis, so the

261
00:20:50 --> 00:20:53
orbitals that are on-axis, d x
squared minus y squared and d

262
00:20:53 --> 00:20:56
z squared are going to
be the most affected.

263
00:20:56 --> 00:20:59
But with tetrahedral, the
ligands are off-axis, so the

264
00:20:59 --> 00:21:02
d orbitals that are also
off-axis are going to

265
00:21:02 --> 00:21:03
be the most affected.
 

266
00:21:03 --> 00:21:06
But they're not going to be as
dramatically affected, so the

267
00:21:06 --> 00:21:09
splitting is actually
smaller in this case.

268
00:21:09 --> 00:21:13
So here, with tetrahedral,
you have the opposite of

269
00:21:13 --> 00:21:16
the octahedral system.
 

270
00:21:16 --> 00:21:19
And you can keep these and
try to convince yourself

271
00:21:19 --> 00:21:25
of that later if you have
trouble visualizing it.

272
00:21:25 --> 00:21:29
So, you'll have more repulsion
between the ligands as negative

273
00:21:29 --> 00:21:32
point charges, and the d
orbitals that are 45 degrees

274
00:21:32 --> 00:21:36
off-axis than you do with
the two d orbitals

275
00:21:36 --> 00:21:39
that are on-axis.
 

276
00:21:39 --> 00:21:44
So here, d x squared minus y
squared and d z squared have

277
00:21:44 --> 00:21:47
the same energy with respect to
each other, they're degenerate.

278
00:21:47 --> 00:21:54
And we have our d y z, x z,
and x y have the same energy

279
00:21:54 --> 00:21:58
with respect to each other,
they are also degenerate.

280
00:21:58 --> 00:22:01
So it's the same sets that
are degenerate as with

281
00:22:01 --> 00:22:08
octahedral, but they're
all affected differently.

282
00:22:08 --> 00:22:13
So now let's look at the energy
diagrams and compare the

283
00:22:13 --> 00:22:17
octahedral system with
the tetrahedral system.

284
00:22:17 --> 00:22:20
Remember an octahedral, we
had the two orbitals going

285
00:22:20 --> 00:22:22
up and three going down.
 

286
00:22:22 --> 00:22:25
The splitting, the energy
difference between

287
00:22:25 --> 00:22:26
them was abbreviated.
 

288
00:22:26 --> 00:22:29
The octahedral crystal field
splitting energy, with a

289
00:22:29 --> 00:22:31
little o for octahedral.
 

290
00:22:31 --> 00:22:35
We now have a t for
tetrahedral, so we have

291
00:22:35 --> 00:22:37
a different name.
 

292
00:22:37 --> 00:22:41
And so here is now
our tetrahedral set.

293
00:22:41 --> 00:22:44
You notice it's the opposite of
octahedral, so the orbitals

294
00:22:44 --> 00:22:49
that were most destabilized in
the octahedral case are now

295
00:22:49 --> 00:22:54
more stabilized down here, so
we've moved down in energy.

296
00:22:54 --> 00:22:58
And the orbitals that are
off-axis, 45 degrees off-axis,

297
00:22:58 --> 00:23:02
which were stabilized in the
octahedral system, because none

298
00:23:02 --> 00:23:05
of ligands were pointing right
toward them, now those ligands

299
00:23:05 --> 00:23:09
are a bit closer so they jump
up in energy, and so we have

300
00:23:09 --> 00:23:15
this swap between the two.
 

301
00:23:15 --> 00:23:18
So, we have some new
labels as well.

302
00:23:18 --> 00:23:24
So, we had e g up here as an
abbreviation for these sets

303
00:23:24 --> 00:23:27
of orbitals, and now that's
just referred to as e.

304
00:23:27 --> 00:23:32
Notice the book in one place
has an e 2, but uses e in all

305
00:23:32 --> 00:23:35
the other places, so just
use e, the e 2 was a

306
00:23:35 --> 00:23:36
mistake in the book.
 

307
00:23:36 --> 00:23:42
And then we have t 2 g
becomes t 2 up here.

308
00:23:42 --> 00:23:45
So we have this slightly
different nomenclature and we

309
00:23:45 --> 00:23:49
have this flip in direction.
 

310
00:23:49 --> 00:23:53
So, the other thing that is
important to emphasize is that

311
00:23:53 --> 00:23:58
the tetrahedral splitting
energy is smaller, because none

312
00:23:58 --> 00:24:00
of those ligands are pointing
directly toward any

313
00:24:00 --> 00:24:01
of the d orbitals.
 

314
00:24:01 --> 00:24:05
So here there is a much larger
difference, here there is a

315
00:24:05 --> 00:24:09
smaller difference, so that's
why it's written much closer

316
00:24:09 --> 00:24:14
together, so that's smaller.
 

317
00:24:14 --> 00:24:19
And because of that, many
tetrahedral complexes are high

318
00:24:19 --> 00:24:21
spin, and in this course, you
can assume that they're

319
00:24:21 --> 00:24:23
all high spin.
 

320
00:24:23 --> 00:24:25
So that means there's a weak
field, there's not a big

321
00:24:25 --> 00:24:31
energy difference between
those orbital sets.

322
00:24:31 --> 00:24:35
And again, we're going to --
since we're going to consider

323
00:24:35 --> 00:24:38
how much they go up and down
in energy, the overall

324
00:24:38 --> 00:24:40
energy is maintained.
 

325
00:24:40 --> 00:24:45
So here we had two orbitals
going up by 3/5, three

326
00:24:45 --> 00:24:47
orbitals going down by 2/5.
 

327
00:24:47 --> 00:24:50
So here, we have three orbitals
going up, so they'll go up in

328
00:24:50 --> 00:24:54
energy by 2/5, two orbitals go
down, so they'll be going

329
00:24:54 --> 00:24:57
down in energy by 3/5.
 

330
00:24:57 --> 00:25:01
So again, it's the opposite
of the octahedral system.

331
00:25:01 --> 00:25:03
It's opposite pretty much in
every way except that the

332
00:25:03 --> 00:25:06
splitting energy is much
smaller, it's not as large

333
00:25:06 --> 00:25:11
for the tetrahedral complex.
 

334
00:25:11 --> 00:25:15
All right, so let's look at an
example, and we're going to

335
00:25:15 --> 00:25:20
consider a chromium, and like
we did before, we have to first

336
00:25:20 --> 00:25:26
figure out the d count, so
we have chromium plus 3.

337
00:25:26 --> 00:25:32
So what is our d count here?
 

338
00:25:32 --> 00:25:36
You know where chromium is,
what its group number --

339
00:25:36 --> 00:25:42
here is a periodic table.
 

340
00:25:42 --> 00:25:45
So what is the d count?
 

341
00:25:45 --> 00:25:46
3.
 

342
00:25:46 --> 00:25:53
So we have 6 minus 3,
3 -- a d 3 system.

343
00:25:53 --> 00:25:58
And now, why don't you tell me
how you would fill in those

344
00:25:58 --> 00:26:02
three electrons in a
tetrahedral case.

345
00:26:02 --> 00:26:56
Have a clicker question there.
 

346
00:26:56 --> 00:27:00
So, notice that in addition to
having electron configurations

347
00:27:00 --> 00:27:02
that are different, the d
orbitals are labelled

348
00:27:02 --> 00:27:29
differently.
 

349
00:27:29 --> 00:27:44
OK, 10 more seconds.
 

350
00:27:44 --> 00:27:47
OK, very good, 80%.
 

351
00:27:47 --> 00:27:49
So, let's take a look at that.
 

352
00:27:49 --> 00:27:53
So down here, we're going to
have then our d x squared minus

353
00:27:53 --> 00:27:58
y squared, d z squared orbitals
up in the top, we have

354
00:27:58 --> 00:28:05
x y and x z and y z.
 

355
00:28:05 --> 00:28:10
Again, the orbitals that are
on-axis are repelled a little

356
00:28:10 --> 00:28:14
less than the orbitals that are
off-axis in a tetrahedral case.

357
00:28:14 --> 00:28:18
And then we put in our
electrons, we start down here.

358
00:28:18 --> 00:28:21
And then one of the questions
is do we keep down here and

359
00:28:21 --> 00:28:26
pair up or go up here, and the
answer is that you

360
00:28:26 --> 00:28:27
would go up here.
 

361
00:28:27 --> 00:28:31
Does someone want to tell me
why they think that's true?

362
00:28:31 --> 00:28:31
Yeah.
 

363
00:28:31 --> 00:28:33
STUDENT: [INAUDIBLE]
 

364
00:28:33 --> 00:28:36
PROFESSOR: Right, because it
has a smaller splitting energy.

365
00:28:36 --> 00:28:38
So, the way that we were
deciding before with the weak

366
00:28:38 --> 00:28:41
field and the strong field, if
it's a weak field, it doesn't

367
00:28:41 --> 00:28:43
take much energy to
put it up there.

368
00:28:43 --> 00:28:45
So you go they don't want to
be paired, there's energy

369
00:28:45 --> 00:28:47
associated with pairing.
 

370
00:28:47 --> 00:28:51
But if there's a really huge
splitting energy, then it takes

371
00:28:51 --> 00:28:54
less energy to pair them up
before you go that big

372
00:28:54 --> 00:28:55
distance up there.
 

373
00:28:55 --> 00:28:58
But in tetrahedral cases, the
splitting energy's always

374
00:28:58 --> 00:29:02
small, so you're just going to
always fill them up singly

375
00:29:02 --> 00:29:05
to the fullest extent
possible before you pair.

376
00:29:05 --> 00:29:09
So this is like a weak field
case for the octahedral system,

377
00:29:09 --> 00:29:12
and all tetrahedral complexes
are sort of the equivalent of

378
00:29:12 --> 00:29:14
the weak field, because the
splitting energy is always

379
00:29:14 --> 00:29:18
small in an octahedral case,
because none of the ligands'

380
00:29:18 --> 00:29:21
negative point charges are
really pointing toward any of

381
00:29:21 --> 00:29:25
those orbitals that much, so
it's not that big a difference.

382
00:29:25 --> 00:29:30
So, here we have this and now
we can practice writing our d

383
00:29:30 --> 00:29:33
to the n electron
configuration.

384
00:29:33 --> 00:29:38
So what do I put here?
 

385
00:29:38 --> 00:29:42
What do I put first?
 

386
00:29:42 --> 00:29:46
So we put the e and then what?
 

387
00:29:46 --> 00:29:47
Yup.
 

388
00:29:47 --> 00:29:51
There are two electrons in the
e set of orbitals, and in the

389
00:29:51 --> 00:29:55
t 2 orbitals, there's one.
 

390
00:29:55 --> 00:29:59
So that is our d n
electron configuration.

391
00:29:59 --> 00:30:03
And then we're also asked how
many unpaired electrons.

392
00:30:03 --> 00:30:16
Unpaired electrons
and that is three.

393
00:30:16 --> 00:30:16
All right.
 

394
00:30:16 --> 00:30:21
So that's not too bad, that's
the tetrahedral case.

395
00:30:21 --> 00:30:23
The hardest part is
probably making your

396
00:30:23 --> 00:30:27
tetrahedral complex.
 

397
00:30:27 --> 00:30:31
Now square planar.
 

398
00:30:31 --> 00:30:34
So again, with the square
planar set you have your square

399
00:30:34 --> 00:30:38
planar model -- we have
a bigger one down here.

400
00:30:38 --> 00:30:43
And the axes is defined such
that we have ligands right

401
00:30:43 --> 00:30:46
along x -- one coming out at
you and one going back, and

402
00:30:46 --> 00:30:50
also ligands right
along the y-axis.

403
00:30:50 --> 00:30:53
So as defined then, we've
gotten rid of our ligands

404
00:30:53 --> 00:30:56
along the z-axis.
 

405
00:30:56 --> 00:30:57
So, what do you predict?
 

406
00:30:57 --> 00:31:04
Which two of these will be
the most destabilized now?

407
00:31:04 --> 00:31:06
What would be the most
destabilized, what

408
00:31:06 --> 00:31:09
do you guess?
 

409
00:31:09 --> 00:31:13
You can hold up your
little sets here.

410
00:31:13 --> 00:31:15
What's the most destabilized,
what's going to go up

411
00:31:15 --> 00:31:19
the most in energy here?
 

412
00:31:19 --> 00:31:22
Yeah, d z squared
minus y squared.

413
00:31:22 --> 00:31:26
What do you predict might
be next, in terms of

414
00:31:26 --> 00:31:29
most unfavorable?
 

415
00:31:29 --> 00:31:30
Yeah, the x y one.
 

416
00:31:30 --> 00:31:35
So these two now are going to
be the most destabilized, with

417
00:31:35 --> 00:31:39
d x squared minus y squared
being a lot more destabilized

418
00:31:39 --> 00:31:42
than just the x y, because
again, those d orbitals

419
00:31:42 --> 00:31:47
are on-axis and these
ligands are on-axis.

420
00:31:47 --> 00:31:51
So, let's take a look
at all of these again.

421
00:31:51 --> 00:31:55
So in the octahedral case,
these were degenerate.

422
00:31:55 --> 00:31:58
That's no longer true,
because there are no ligands

423
00:31:58 --> 00:32:00
along the z-axis anymore.
 

424
00:32:00 --> 00:32:03
So we took those off in going
from the octahedral to the

425
00:32:03 --> 00:32:07
square planar, so you have much
less repulsion, but with the d

426
00:32:07 --> 00:32:12
x squared minus y squared, you
still have a lot repulsion.

427
00:32:12 --> 00:32:17
so then if we start building up
our case, and this diagram is,

428
00:32:17 --> 00:32:19
I think, on the next page of
your handout, but I'm going to

429
00:32:19 --> 00:32:21
start building it
all up together.

430
00:32:21 --> 00:32:26
So now d x squared, y squared
is really high up, it's very

431
00:32:26 --> 00:32:29
much more destabilized
than anybody else.

432
00:32:29 --> 00:32:32
D z squared, on the
other hand, is down.

433
00:32:32 --> 00:32:35
It's not -- it would be
stabilized compared -- it's

434
00:32:35 --> 00:32:40
not nearly as destabilized
as the other system.

435
00:32:40 --> 00:32:44
So then we go back
and look at these.

436
00:32:44 --> 00:32:48
You told me that d x y would
probably be next, and

437
00:32:48 --> 00:32:50
that's a very good guess.
 

438
00:32:50 --> 00:32:53
You see you have more repulsion
than in the other two, because

439
00:32:53 --> 00:32:56
the other orbitals have
some z component in them.

440
00:32:56 --> 00:33:00
So you have less repulsion than
d x squared minus y squared,

441
00:33:00 --> 00:33:04
because it's 45 degrees off,
but still that one is probably

442
00:33:04 --> 00:33:07
going to be up a little bit
more in energy than

443
00:33:07 --> 00:33:08
the other set.
 

444
00:33:08 --> 00:33:13
These two here are stabilized
compared to the others, so

445
00:33:13 --> 00:33:14
they're somewhere down here.
 

446
00:33:14 --> 00:33:18
Now the exact sort of
arrangement can vary a little

447
00:33:18 --> 00:33:22
bit, but the important points
are that the d x squared minus

448
00:33:22 --> 00:33:26
y squared is the most
destabilized, d x y would be

449
00:33:26 --> 00:33:31
next, and the other are
much lower in energy.

450
00:33:31 --> 00:33:34
And we're not going to do this
how much up and down thing,

451
00:33:34 --> 00:33:38
like the 3/5 and the
2/5 because it's more

452
00:33:38 --> 00:33:40
complicated in this case.
 

453
00:33:40 --> 00:33:43
So just the basic rationale you
need to know here, not the

454
00:33:43 --> 00:33:52
exact energy differences
in this particular case.

455
00:33:52 --> 00:33:58
OK, so now we've thought about
three different kinds of

456
00:33:58 --> 00:34:01
geometries -- octahedral,
tetrahedral, and

457
00:34:01 --> 00:34:02
the square planar.
 

458
00:34:02 --> 00:34:07
You should be able to
rationalize, for any

459
00:34:07 --> 00:34:10
geometry that I give
you, what would be true.

460
00:34:10 --> 00:34:14
If I tell you the geometry and
how it compares with our frame,

461
00:34:14 --> 00:34:19
with our axis frame of where
the z-axis is, you should be

462
00:34:19 --> 00:34:21
able to tell me which
orbital sets would be

463
00:34:21 --> 00:34:24
the most destabilized.
 

464
00:34:24 --> 00:34:28
And to give you practice,
why don't you try

465
00:34:28 --> 00:34:29
this one right here.
 

466
00:34:29 --> 00:34:35
So we have a square pyramidal
case as drawn here with the

467
00:34:35 --> 00:34:40
axes labeled z, y and x,
coming in and coming out.

468
00:34:40 --> 00:34:46
Tell me which of the following
statements are true.

469
00:34:46 --> 00:34:51
And if you want, you can take
your square planar and turn it

470
00:34:51 --> 00:35:54
into the geometry
to help you out.

471
00:35:54 --> 00:36:10
Let's just take
10 more seconds.

472
00:36:10 --> 00:36:11
All right.
 

473
00:36:11 --> 00:36:13
That was good.
 

474
00:36:13 --> 00:36:15
People did well on
that question.

475
00:36:15 --> 00:36:25
So, if we consider that we
had the top two are correct.

476
00:36:25 --> 00:36:29
So, if we consider the d z
squared, now we've put a ligand

477
00:36:29 --> 00:36:33
along z, so that is going to
cause that to be more

478
00:36:33 --> 00:36:37
destabilized for this geometry
rather than square planar,

479
00:36:37 --> 00:36:42
which doesn't have anything in
the z direction. ah And then in

480
00:36:42 --> 00:36:47
terms, also, other orbitals
that have a component along z

481
00:36:47 --> 00:36:52
are going to be affected a
little bit by that, but our

482
00:36:52 --> 00:36:56
other one here is not going to
be true, so we just have all of

483
00:36:56 --> 00:36:58
the above is not correct,
so we have this one.

484
00:36:58 --> 00:37:02
So if we had up those, that's
actually a pretty good score.

485
00:37:02 --> 00:37:07
And so you could think about,
say, what would be true of a

486
00:37:07 --> 00:37:11
complex that was linear along
z, what would be the most

487
00:37:11 --> 00:37:13
stabilized, for example.
 

488
00:37:13 --> 00:37:16
So these are the kinds of
questions you can get, and

489
00:37:16 --> 00:37:20
I think there are a few
on the problem-set.

490
00:37:20 --> 00:37:24
All right, so let's come
back together now and talk

491
00:37:24 --> 00:37:26
about magnetism again.
 

492
00:37:26 --> 00:37:30
So, we said in the beginning
that magnetism can be used to

493
00:37:30 --> 00:37:35
figure out geometry in, say, a
metal cluster in an enzyme, and

494
00:37:35 --> 00:37:39
let's give an example of
how that could be true.

495
00:37:39 --> 00:37:44
So, suppose you have a nickel
plus 2 system, so that would be

496
00:37:44 --> 00:37:49
a d 8 system, so we have group
10 minus 2 or d 8, and it was

497
00:37:49 --> 00:37:51
found to be diamagnetic.
 

498
00:37:51 --> 00:37:56
And from that, we may be able
to guess, using these kinds of

499
00:37:56 --> 00:37:59
diagrams, whether it has
square planar geometry,

500
00:37:59 --> 00:38:03
tetrahedral geometry,
or octahedral geometry.

501
00:38:03 --> 00:38:08
We can predict the geometry
based on that information.

502
00:38:08 --> 00:38:11
Let's think about
how that's true.

503
00:38:11 --> 00:38:14
We have a d 8 system.
 

504
00:38:14 --> 00:38:17
Think about octahedral
for a minute.

505
00:38:17 --> 00:38:24
Are there two options for how
this might look in this case?

506
00:38:24 --> 00:38:26
Is there going to be a
difference in electron

507
00:38:26 --> 00:38:32
configurations if it's a weak
field or a strong field?

508
00:38:32 --> 00:38:36
So, write it out on your
handout and tell me whether

509
00:38:36 --> 00:38:54
it would be true, think
about it both ways.

510
00:38:54 --> 00:38:58
Is there a difference?
 

511
00:38:58 --> 00:39:00
So, you would end up
getting the same thing

512
00:39:00 --> 00:39:01
in this particular case.
 

513
00:39:01 --> 00:39:05
So if it's a weak field and
you put in 1, 2, 3, then jump

514
00:39:05 --> 00:39:09
up here, 4, 5, and then you
have to come back, 6, 7, 8.

515
00:39:09 --> 00:39:13
Or you could pair up all the
ones on the bottom first and

516
00:39:13 --> 00:39:16
then go up there, but you
actually get the same result no

517
00:39:16 --> 00:39:21
matter which way you put them
in, the diagram looks the same.

518
00:39:21 --> 00:39:24
So it doesn't matter in this
case if it is a weak or strong

519
00:39:24 --> 00:39:27
field, you end up with those
number of electrons with the

520
00:39:27 --> 00:39:31
exact same configuration.
 

521
00:39:31 --> 00:39:33
So, we know what
that looks like.

522
00:39:33 --> 00:39:36
Well, what about square planar.
 

523
00:39:36 --> 00:39:38
So let's put our
electrons in there.

524
00:39:38 --> 00:39:41
We'll start at the bottom,
we'll just put them in.

525
00:39:41 --> 00:39:44
I'm not going to worry too much
about whether we can jump up or

526
00:39:44 --> 00:39:48
not, we'll just go and pair
them up as we go down here, and

527
00:39:48 --> 00:39:52
then go up here, and now we've
put in our eight electrons.

528
00:39:52 --> 00:39:56
So, how close these are, we're
just going to put them all in.

529
00:39:56 --> 00:39:59
We're just going to be very
careful not to bump up any

530
00:39:59 --> 00:40:04
electrons there unless we
absolutely have to, because d x

531
00:40:04 --> 00:40:08
squared minus y squared is very
much more destabilized in the

532
00:40:08 --> 00:40:11
square planar system, so we're
going to want to pair all

533
00:40:11 --> 00:40:15
our electrons up in those
lower energy orbitals.

534
00:40:15 --> 00:40:18
So even if we sort of
did it a different way,

535
00:40:18 --> 00:40:19
that's what we would get.
 

536
00:40:19 --> 00:40:22
So we're going to want to pair
everything up before we go

537
00:40:22 --> 00:40:25
up to that top one there.
 

538
00:40:25 --> 00:40:26
So there's our square planar.
 

539
00:40:26 --> 00:40:28
Well, what about tetrahedral.
 

540
00:40:28 --> 00:40:31
How are we going
to fill these up?

541
00:40:31 --> 00:40:37
Do we want to pair first, or
we do want to put them to the

542
00:40:37 --> 00:40:40
full extent possible singly?
 

543
00:40:40 --> 00:40:43
Single, right, it's going to be
a weak field, there's not a big

544
00:40:43 --> 00:40:46
splitting here between these,
so we'll put them in, there's

545
00:40:46 --> 00:40:53
1, 2, 3, 4, 5, 6, 7, 8.
 

546
00:40:53 --> 00:40:55
All right, so now we can
consider which of these will

547
00:40:55 --> 00:40:58
be paramagnetic and which
will be diamagnetic.

548
00:40:58 --> 00:41:01
What's octahedral?
 

549
00:41:01 --> 00:41:05
It's paramagnetic, we
have unpaired electrons.

550
00:41:05 --> 00:41:08
What about square planar?
 

551
00:41:08 --> 00:41:10
Square planar's diamagnetic.
 

552
00:41:10 --> 00:41:11
And what about tetrahedral?
 

553
00:41:11 --> 00:41:14
Paramagnetic.
 

554
00:41:14 --> 00:41:20
So, if the experimental data
told us that a nickel center in

555
00:41:20 --> 00:41:23
an enzyme was diamagnetic, and
we were trying to decide

556
00:41:23 --> 00:41:27
between those three geometries,
it really seems like square

557
00:41:27 --> 00:41:31
planar is going to
be our best guess.

558
00:41:31 --> 00:41:34
And so, let me show
you an example of a

559
00:41:34 --> 00:41:39
square planar system.
 

560
00:41:39 --> 00:41:44
And so this particular nickel
is in a square planar system.

561
00:41:44 --> 00:41:50
It has four ligands that are
all in the same plane, and it

562
00:41:50 --> 00:41:54
is a square planar center for a
nickel, so that's one example.

563
00:41:54 --> 00:41:58
And this is a cluster
that's involved in life

564
00:41:58 --> 00:42:01
on carbon dioxide.
 

565
00:42:01 --> 00:42:04
All right, so that's
different geometries,

566
00:42:04 --> 00:42:05
you're set with that.
 

567
00:42:05 --> 00:42:09
Monday we're going to talk
about colors of coordination

568
00:42:09 --> 00:42:12
complexes, which all have to do
with the different geometries,

569
00:42:12 --> 00:42:16
paired and unpaired electrons,
high field, low spin,

570
00:42:16 --> 00:42:19
strong field, weak field.
 

571
00:42:19 --> 00:42:21
Have a nice weekend.
 

572
00:42:21 --> 00:42:22