Advanced Transition Metal Chemistry – Classification of Ligands

Prof M. S. Balakrishna
Department of Chemistry
Indian Institute of Technology – Bombay

Lecture – 27
Classification of Ligands - Hydrogen

Hello everyone. I welcome you once again to MSB lecture series on transition metal
chemistry. In my previous two lectures, I gave the method of preparation of important
compounds useful in doing substitution reactions in coordination chemistry and also their
utility in organic transformation as homogeneous catalysts or precursors. So, let me now try
to do the classification of ligands.

As you know, ligands can be classified in several ways. The simplest way of classifying all
ligands into two categories is classical or simple donor ligands, and nonclassical ligands or pi
bonding and pi acceptor ligands. So, what are the difference between classical or simple
donor ligands and nonclassical ligands, besides having sigma donor capability, they also can
be pi donors or pi acceptors.

So, these classical or simple donor ligands act as electron pair donors to acceptor ions or
molecules and form complexes with all types of Lewis acids, metal ions or molecules
including main group elements. Now how about nonclassical ligands? They are also called as
pi-bonding or pi acid ligands. They form largely with the transition metal atoms and we will
come across a special interaction between the metal and the ligands under nonclassical
ligands.

And these ligands act as both sigma donors and pi acceptors due to the availability of empty
orbitals of suitable symmetry and energy, comparable to those of metal nonbonding orbitals.
For example, if you consider octahedral complexes, here t2g remains as nonbonding and t2g
orbitals you know already that they are dxy, dxz and dyz and they have pi symmetry and they
can interact with suitable pi acceptor orbitals of ligands and back bonding takes place.

For example, consider a tertiary phosphine and ammonia, both can act as bases towards H+
but phosphorus differs from N because in teritiary phosphines, we come across low energy
sigma star (σ*) orbitals essentially of antibonding in nature, whereas N does not have such
orbitals for back bonding. So, that means sigma star orbitals of tertiary phosphines can
interact with the t2g or nonbonding orbitals of the metal complex and accept electrons which
are not utilized in metal to ligand bond formation and hence it can reinforce the metal to
phosphorus bond that is what we call it as back bonding.

Let us consider carbon monoxide that do not have measurable basicity to protons, yet readily
reacts with metals like nickel that have high heats of formation or high heats of atomization
to give compounds such as nickel tetracarbonyl.

Ligands may also be classified electronically depending upon how many electrons that they
contribute to a central atom. That means apart from classifying them into classical,
nonclassical, one can also classify ligands depending upon how many electrons they are in a
position to donate or contribute to the central atom. For example, if a ligand is capable of
giving only 2 electrons that is called monodentate ligand.

Or if it has 2 donor atoms with each one a pair of electrons is called bidentate ligand or it can
be tridentate ligand, tetradentate or it can be a polydentate. So, atoms or groups that can form
a single covalent bond, one electron donors. For example, if you take F–, SH–, CH3– consider
they are one electron donors, Cl also for that matter. Of course, I had already discussed it and
classified them in my previous lectures. Any compound with an electron pair or 2 electron
donors, For example, ammonia, water, tertiary phosphine, carbon monoxide, etc.
(Refer Slide Time: 04:34)
And groups that can form a single bond at the same time donate an electron pair are called 3
electron donors. We also come across many. An ideal and classical example is acetate here.
Acetate you can see, if you take acetic acid and remove one hydrogen it forms anionic and
now it forms a covalent bond here and then this carbon monoxide, this oxygen also has a pair
of electrons, two pairs of electrons are there.

One of that when can rotate in this fashion that it can give, since here it shows two resonance
structures we represent acetate in this fashion having electron distribution or this pair of
electrons are delocalized and it becomes a monoanionic and this is a 3 electron donor in the
neutral method, whereas in this one it is a 4 electron donor because O– is there and CO, so
this is essentially 4 electron donor, according to ionic method.

In neutral method it is 3 electron donor, just dot will represent here unless it takes a negative
charge it is not a 4 electron donor. So, now, we also come across two donor atoms in a
molecule, they are called bidentate ligands. Bidentate ligands when they bond entirely to one
metal atom are termed as chelate, and if they are bonding to two different metal atoms, they
are called bridging.

Of course, we are also using the terms kappa (κ) for chelate and mu (µ) we are using for
bridging that already I told you in the beginning. Bidentate ligands on chelation can form 3,
4, 5 or even 5 membered rings according to the size of the chelate ring and further
classification is according to the nature of donor atoms of the ligand. So, that means if you
take any species and if you identify that donor atom, then we can classify according to that
donor atom.

That means we may classify them as carbon, nitrogen, oxygen, phosphorus, sulfur or
hydrogen donor atoms. So, under oxygen, we come across several, the simplest one being
water. But also, if you take triphenylphosphine oxide, here phosphorus no longer has a pair of
electron because phosphorus is in +5 state; oxygen has a pair of electrons so that
triphenylphosphine oxide is also an oxygen donor, of course when we go for hard acids and
hard base concepts, we come across sulfate, acetate, carboxylate, all those things come.
(Refer Slide Time: 06:49)
Under carbon, we come across a variety of ligands, a few I have shown here.
Cyclopentadienyl, like allyl group or carbon monoxide and also neutral ligand such as
benzene, etc. For nitrogen nitrate, is there, nitrosyl is there. Primary, secondary and tertiary
amines are there and we have plenty of pyridine ligands besides that we have several
macrocycles having nitrogen as donor atoms.
(Refer Slide Time: 07:14)

So, here I have listed some important compounds with their abbreviation and formula to
make you familiar. I must have shown this one in my previous lecture. However, let me
continue telling something about these things as well, now before I take up the classification
of ligands by donor atoms. So, hydrido we call is H. Of course carbonyl CO, cyano we call
CN–, methyl CH3– and cyclopentadienyl Cp– or C5H5–.
Carbonato is there [CO3]2–and ammine we call ammonia NH3 and pyridine is there and then
bipyridine is there. Of course, in case of bipyridine we come across two types of bipyridines,
one is 2,2’-bipyridine and another one is 4,4’- bipyridine. 4,4’- Bipyridine can only act as a
bridging ligand whereas 2, 2’-bipyridine can comfortably chelate to a metal centre.

And triphenylphosphine is there and of course under here we come across several phosphorus
compounds, I shall elaborate more when we go to phosphorus as donor atom. And aqua we
call water and acetylacetonato is also there. it is anionic similar to acetate and thiocyanato
and chloro and edta is a hexadentate ligand.
(Refer Slide Time: 08:31)

And then let us compare the donor and acceptor capability of several ligands with respect to
carbon monoxide. Many of these ligands are isoelectronic with carbon monoxide. Of course,
we all know that carbon monoxide is a better sigma donor and also a better pi acceptor.
Thiocarbonyl does not have an independent existence. However, this can be generated in situ
starting from appropriate precursors or starting materials to establish a metal to CS bond.

And when you make this one, this is a better sigma donor and it is a better acceptor than even
CO. And N2, dinitrogen we come across many dinitrogen complexes, I shall discuss more
about that one under nitrogen. And of course, we all know that this is very inert molecule, as
a result is a worse sigma donor and is a worse pi acceptor and it is very challenging to
coordinate N2 to metal complexes.
And cyanide, very good sigma donor, but it is a poor pi acceptor. I shall tell you why it is a
poor pi acceptor, it is already negatively charged, as a result, what happens, it is a poor pi
acceptor. CNR is a good sigma donor and also good pi acceptor and nitrosyl good sigma
donor and good pi acceptor.
(Refer Slide Time: 09:45)

And then as I mentioned carbon monoxide is good sigma donor and a very strong pi acceptor.
Then how to distinguish, to what extent a carbon monoxide has taken electrons from metal to
its antibonding orbital. So that can be readily monitored using IR spectroscopy by looking
into the CO stretching frequencies. If you have terminal carbonyl groups, in that case what
happens depending upon how many carbon monoxides are there and what is the geometry,
the stretching frequency can range from 1850 to 2100 cm –1.

And when they are bridging what happens it will be having double bond character as a result
stretching frequency drops significantly to be in the range of 1700 to 1850 cm –1. And when it
is bridging three metal centres, it further drops and one can observe stretching frequency
between 1600 to 1700 cm –1. And of course, one should know that free CO has stretching
frequency of 2143 cm –1. And as I mentioned CS is a better sigma donor and also a better pi
acceptor and free CS is very unstable.

But at low temperature if you monitor, it shows a stretching frequency of 1273 cm –1 and the
terminal CS will be having stretching frequency between 1160 to 1410 cm –1. And when it is
bridging, the same stretching frequency will drop to 1100 to 1160 cm –1. And then when it is
bridging three metal centres it further drops and appears in the range of 1040 to 1080 cm –1.
And NO is a worse sigma donor and it is a better pi acceptor.

And of course, again it can show two different types of binding, one is linear, one is bent.
When it's linear it is a 3 electron donor, when it is a bent it is 1 electron donor. So here when
it is linear and whether it is linear or bent, one can also analyse by simply doing electron
count. On the other hand, the experimental one can also know by simply taking IR spectrum
of that complex. For linear NO, stretching frequency appears around 1600 to 1850 cm –1, for
bent it comes around 1500 to 1700 cm –1.

That means characterizing these compounds and identifying the nature of coordination should
not be a problem because IR comes very handy in these cases. N2 as I mentioned is a worse
sigma donor and worse pi acceptor and it is very challenging to make these complexes,
nevertheless I will show you preparation of these compounds and what kind of metals one
should look for to make dinitrogen complexes.

And free N2 has Raman active band at 2331 cm –1. And of course, when it is binding
terminally with one nitrogen donating this lone pair to metal, the stretching frequency will be
700 to 2200 cm –1. And CN– is a good to moderate and of course here also one can look at
stretching frequency, there should not be a problem. And CNR (isocyanide) is a stronger
sigma donor, but weak pi acceptor. And in this case, the stretching frequency comes around
2000 to 2200 cm –1.

Here HOMO highest occupied molecular orbital is much more antibonding than that of CO,
one should remember when we look into the activity. And teritiary phosphine is a good sigma
donor and stronger pi acceptor. And of course, it is very interesting to compare the donor and
acceptor ability of carbon monoxide and phosphine. Let me do it at appropriate juncture as
we progress with this one.

It is very interesting and we can always say why teritiary phosphine is a better ligand
compared to carbon monoxide, we can discuss those things in length, let me do it at later
stage.
(Refer Slide Time: 13:32)
So, now let me show you a few examples of all types of ligands we come across before I take
up the classification of ligands by donor atom starting with hydrogen ligands. This acac you
can see here because of tautomerism what happens, it becomes a double bond shifted here
and it becomes O- and again O– can be here or here, so again, the negative charge is
delocalized and it acts as a monoanionic ligand.

And also, it is a 4 electron donor in this fashion. Similarly, oxalate is dianionic and then one
can also go for diethylthiocarbamate ion here and salicylaldehyde anion again is very similar
to acetate and 8-hydroxyquinol O– anionic and neutral it can be. And then dimethylglyoxime
also can be anionic and phenylenebis(dimethylarsine) this is 1,2-substituted one is a very nice
bidentate ligand.

And also, we have several bidentate ligands phosphines, this is dppm, and
diphenylphosphinomethane, it is 1,2-bis(diphenylphosphino)methane and this is
diphenylphosphinoamine and of course here R can be H or any other alkyl or aryl group. This
is also another interesting oxygen bridged ligand.
(Refer Slide Time: 14:53)
And of course, as I mentioned, we have plenty of nitrogen based cyclic and acyclic ligands.
So, there are numerous examples of cyclic ligands of nitrogen, the simplest one being
pyridine, pyrimidine, pyrazine, triazole, pyrrole of course it can be an ionic and pyrazole,
imidazole is there. And then 2,2’-bipyridine a chelating ligand, 4,4’-bipyridine ideal for
bridging and also we have 1,10-phenanthroline.

This is another interesting ligand, terpyridine and this is naphthyridine and this is purine,
adenine and also this is hexapyridine and also it is a torand. So, we have plenty of nitrogen
donor ligands. Apart from this, we also have classical macrocyclic ligands which are widely
seen among biologically active molecules.
(Refer Slide Time: 15:48)
For example, this one is also ethylene diamine derived bisphosphine and this is the famous
EDTA, ethylene diamine tetra acetic acid and then it can form readily anionic, as a result it
can be tetra anionic and then this will be hexadentate ligand. And then we have this acac we
have. And then as I mentioned several nitrogen macrocycles are there, this is one such
compound, this is phthalocyanine and this one can be prepared only in situ and this also
called encapsulating ligand, one can make something like this here.

And then porphyrin, if you want to know the difference between several macrocyclic ligands
if you simply look into the porphyrin it has two N and two NH one opposite sides, that means
it can be dianionic and it can stabilize metal in +2 to state and corrole will be having one
nitrogen and three NH will be there trianion, and homoporphyrin if you take, one CH2CH2
bridge will be there instead of one CH2 here that is called homoporphyrin. And porphycene
opposite ends have pyrrole links.

I have given the information about those, one can look into the structures of some of these
nitro macrocycles in standard textbooks. So, in this porphycene opposite ends have direct
pyrrole links and two CH2CH2 links on other two ends. And also we have corrphycene in that
one direct and 3CH2CH2 links will be there. And in case of hemiporphycene we have 2
adjacent CH2 and one direct CH2CH2 links will be there. The links I am talking about is these
things that separates pyrrole groups.
(Refer Slide Time: 17:31)

And this I have done it again, I shall just tell you about pure sigma donors. These are pure
sigma donors, they do not have pi acceptor or pi donor capabilities. And then we have sigma
donors and pi donors, all these halogens and NCO, NCS, N3–, OH–, OR, acac, etc. They are
sigma donors as well as pi donors.
We have sigma donors and pi acceptors, very important ligand system, they are also called as
nonclassical, unfortunately. They are carbon monoxide, cyano, NO, N2, RNC, PR3 and one
can also write a spectrochemical series for these things by looking into their donor and
acceptor capabilities. Similarly, among pi donors and pi acceptors, we have several carbon
donor ligands such as Cp–, C6H6, C7H7+ and ethylene and acetylene. They are called pi
donors and pi acceptors because these pi electrons are going to the metal as sigma that is the
reason they are called pi donors.

One of the bonds in a double bond will be donated to the metal in the form of 2 electrons that
is the reason they are called pi donors and pi acceptors, but however this pi bond whatever
that is established is sigma in nature.
(Refer Slide Time: 18:53)

Let me give an extended spectrochemical series also, before I begin the discussion. It is very
difficult to remember the relative positions, nevertheless by looking into the nature of ligands
we should be able to tell whether a given ligand is a strong field ligand or a weak field ligand,
relatively we should be able to tell. We should be familiar with the nature of the ligands.
(Refer Slide Time: 19:17)
So, now let us start the classification of ligands by donor atoms. To begin with, let us
consider hydrogen, the simplest donor atom. Typical ligands of hydrogen donor are hydrides,
dihydrogen and also several main group hydrides. For example, BH4-, AlH4-, etc. First
hydride complex was iron tetracarbonyl hydride and then this was reported by Walter Hieber
and coworker in 1931. He also reported this cobalt hydride having 4 carbon monoxide.

So German documentation has indicated that this complex was used in hydroformylation
much earlier. In mid 50s, hydrides such as rhenium hydride by Wilkinson and also this was
made by Fischer and also this one platinum hydride was made by Chat. So, all these hydrides
of rhenium, molybdenum and platinum were made in 1950s by these respective chemists.
First dihydrogen complex is MoH2(CO)3(PCy3)2] was reported by Kubas in 1984.
(Refer Slide Time: 20:29)
So, let us look into the coordination modes of hydrogen. There can be terminal hydrogen also
something like this, so this is terminal. Apart from this terminal and standard, we can also see
hydrogen bridging two metal centres and of course you can recall the structure of borane
where we form three-centre two-electron bond, in the same way here also it establishes a
three-centre two-electron bond, this one binds with suitable orbitals of both the metal centres.

And of course, you can also have two bridging hydrides in this fashion without metal-metal
bond or with metal-metal bond. And three hydrides linking or bridging two metal centres are
also known. And also we can have mixed bridging ligands such as halides and also hydrogen.
And we can also have something like this hydrogen bridging three metal centres. These are
some common coordination modes or binding modes of hydrogen among metal hydride
complexes.
(Refer Slide Time: 21:37)

The affinity for hydrogen is very small or zero for d-block elements with an exception of
palladium and also palladium silver alloy and copper complex. So, the rate of diffusion of
hydrogen is very high through the metal membrane of these metals compared to any other
metals among transition element series. Studies have shown the presence of
palladium-hydride phases. That is the reason palladium on carbon is widely used in
hydrogenation reactions.
(Refer Slide Time: 22:08)
So, now let us look into the binding modes of hydrogen. And of course, when you look into
H2 molecule, we have a pair of electron that establishes H-H bond, that pair of electron can be
readily donated to M through sigma donation, very similar to olefines, and this is pi donation.
On the other hand, this sigma star is empty, the sigma star of H2 can be comparable to the
sigma star of PR3.

So, that means the sigma star can also interact with suitable metal pi symmetry orbitals such
as dxy, dxz and dyz to establish back bonding, that is from metal to hydrogen antibonding. That
means, hydrogen can act as a sigma donor as well as a pi acceptor. More details will be
provided while considering oxidative addition of H2 to a square planar complex.

When I go to oxidative addition reductive elimination reaction, I shall elaborate more about
how one can manipulate hydrogen coordination to metal centre for the purpose of
hydrogenation of olefins and other unsaturated organic compounds, that you cannot do
conventionally, even at a very high temperature. So, let me stop at this juncture and continue
discussing more about hydrogen as donor atom with examples and method of preparation and
properties and bonding, etc., in my next lecture. Until then, have an excellent time reading
chemistry.