Reagent Friday: Palladium on Carbon (Pd/C)

It’s almost been 100 years since Paul Sabatier was

awarded the 1912 Nobel prize for his discovery that
hydrogen gas will add to alkenes (among other molecules,
such as CO2) when both are passed over finely powdered
metals. This general reaction – “hydrogenation” – by
which C–C (π) bonds are broken and C–H bonds are
formed, was an extremely useful discovery that is still
carried out on multi-ton scale today. The main industrial
use of hydrogenation is in preparation of saturated
fats from unsaturated fats, which makes them less likely
to spoil. What lasts longer in your fridge, butter or
margerine? You can thank the hydrogenation for that.
Hydrogenation is also to blame for trans fats, but that’s
another story.
While finely divided nickel was originally Sabatier’s
catalyst of choice, extensive experimentation with other
metals have shown that palladium, platinum, rhodium, and
other “late” metals are also capable of assisting this
transformation. Although the first image of platinum that
might come to mind is that of a gleaming metal, in practice
these reactions are very surface area dependent, and
work much better when the finely divided, powdered form
is used. This is generally called the “black” form. I can’t
find a good picture of platinum black but here is a picture
of the related platinum oxide. It’s pretty far from what you
might expect to see at first glance for a “shiny” element
like platinum.
In practice it can be a bit of a pain to weigh out trace
amounts of expensive platinum or palladium metal to run
reactions on small scale, so it’s more convenient to use a
prepared mixture where the metal has been absorbed on
a cheap, high surface area material like charcoal. The
resulting palladium on carbon (Pd/C) or platinum on
carbon (Pt/C) is the bench chemists’ workhorse reagent
for hydrogenation reactions.

[One note here: for our purposes, palladium on carbon

(Pd/C), platinum on carbon (Pt/C) or just plain palladium
(Pd) or platinum (Pt) are all equivalent to each other. That
is to say that they all do exactly the same reactions. There
are subtle differences in reactivity between these
reagents, but we needn’t concern ourselves with that here.
]
So how does it get used? All kinds of useful ways.

First of all as already described Pd/C will reduce alkenes

to alkanes when hydrogen is also present. It’s important to
note that the to hydrogens from the alkene are delivered
syn (i.e. the same face of the alkene).
Pd/C and hydrogen will reduce alkynes all the way to
alkanes – that is, two equivalents of H2 are added.
Contrast that to Lindlar’s catalyst, which only adds one
equivalent of H2 (but also in syn fashion).

Pd/C and hydrogen will also reduce other multiple bonds,

such as NO2 (nitro groups), CN (nitriles) and C=NR
(imines).

Finally, if enough heat and pressure is added, Pd/C and

hydrogen gas will also reduce aromatic groups such as
benzene. Note that this reaction is considerably more
difficult than reducing a “normal” double bond due to the
greater stability of the aromatic benzene ring.
So how does it work?

It’s important to note that Pd/C is a catalyst in all of these

reactions, meaning that it accelerates the rate of reactions
but is not itself consumed. That is, Pd/C is a lot like a
matchmaker who brings couples together, but never gets
married himself. Another analogy is to think of the surface
of Pd/C as kind of like a singles bar, where hydrogen and
alkenes (or other organic compounds) meet, react, and
leave together. Note that the hydrogen is always delivered
to the same face of the alkene (“syn” addition).

It’s also possible to substitute the heavy isomer of

hydrogen (deuterium, D) for H2, which will deliver D to the
alkene.
Reagent Friday: Sodium (Na)

Today’s topic, sodium metal is a pretty notorious reagent. You might know it from Youtube
as “That solid that you drop in water and blows things up, a property it shares
with potassium and other alkali metals.
Sodium has lots of uses in organic chemistry. Sodium metal has but a lone electron in its
valence shell, and gives it up quite easily to any molecule that will accept. That includes
water: what’s happening when you drop sodium metal into water is that H2O is being
reduced to hydrogen gas, forming sodium hydroxide in the process. Sodium can also be
used to reduce many types of organic compounds such as alkynes and aromatic
compounds among many others not discussed here.

What it’s used for: a strong reducing agent, will reduce alkynes to trans-alkenes. Will also
form hydrogen gas when added to alcohols, resulting in alkoxides. Will also reduce aromatic
groups to alkenes (the Birch reduction). Sodium metal will generally not reduce alkenes.
Let’s look at the first example: reduction of alkynes to trans-alkenes. Sodium will dissolve in
liquid ammonia (boiling point -33 °C) producing a beautiful deep blue color. When alkynes
are present, they will be reduced to the trans (i.e. E) alkene. This makes Na/NH3 a useful
companion to the Lindlar reduction of alkynes, which gives cis-alkenes.

As mentioned previously, sodium metal will also convert alcohols to alkoxides (remember:
alkoxides are the conjugate bases of alcohols). In the process this liberates hydrogen gas,
so it must be done with great caution and advisably under an oxygen-free atmosphere. This
iss a useful way to make the conjugate base of an alcohol without worrying about the
conjugate acid hanging around in solution, since the only byproduct is hydrogen gas.
Finally, sodium metal in ammonia (NH3) containing several equivalents of t-butanol will
reduce aromatic compounds to (non-conjugated) dienes. This useful reaction is called
the Birch reduction. Note that the pattern depends on whether the substituent on the
aromatic group is electron donating (such as OCH3) or electron withdrawing (CO2Me).

How it works – we’ll just discuss the alkyne reduction here for now, but reduction of the
alkyne by sodium results in breakage of the C-C double bond and formation of an anion
adjacent to a radical. The radical that is formed can interconvert between its cis and trans
form, but the trans is generally more stable due to steric factors. The anion is then
protonated by NH3 (the only acid present in solution) to give the vinyl radical, which is then
reduced by a second equivalent of Na to give a second anion. This is then (you guessed it)
then converted to the alkene by protonation with a second equivalent of NH3. So the net
process gives a trans-alkene and two equivalents of NaNH2.
Real life tips. Since sodium metal is a solid, many of its reactions are surface-area
dependent. That means that it is most effective as a reagent when cut up into fine strips or
wires rather than chunks. As you can imagine, a reagent that reacts violently with water is
potentially very hazardous. Sodium is notoriously dangerous when used to remove traces
of water from solvents in distillation setups: chunks can be passivated with a surface layer
of NaOH, and scratching the surface of the material during quench will then expose reactive
sodium metal, which can then react rapidly with the quenching agent, leading to explosions
and fires. Potassium is even worse for this. Google “solvent still fire” and you will get the
idea.
Reagent Friday: Raney Nickel

Named reagents have a slightly mysterious air to them, conjuring up (for me, anyway) the
image of a lone scientist working long hours for an elusive goal, until they finally have
that “Eureka” moment. In this vein, while “Rearden metal” may solely be a work of fiction,
“Raney Nickel” is very real. Raney nickel is an alloy of aluminum and nickel, which has
subsequently had much of the aluminum removed through a leaching process with
sodium hydroxide (NaOH). The remaining alloy has a very high surface area and also
contains hydrogen gas (H2) adsorbed on the nickel surface.
What it’s used for: Like palladium on carbon (Pd/C) and platinum on carbon (Pt/C),
Raney nickel can be used for the hydrogenation of alkenes and alkynes. But what Raney
nickel is used most for is its unusual property of reducing C-S bonds to C-H bonds. It’s
this second application that can make Raney nickel uniquely useful. When combined with
the formation of a thioketal from a ketone, this can serve as an alternative means of
converting ketones to alkanes (just like the Wolff-Kishner reaction). For a real-life
application of this reagent in the synthesis of erythromycin by Nobel Laureate R.B.
Woodward, see the great discussion by B.R.S.M. here.

Here’s the second application of Raney nickel – as a catalyst for hydrogenation. Note
that in this case we don’t necessarily need to add hydrogen gas (although it helps) –
Raney nickel is usually obtained in its “activated” form, where the hydrogen is already
adsorbed onto it.

How it works: “For our purposes” (love this phrase) it’s not so important exactly how
Raney nickel works. There’s something mysterious about it: the aluminum is crucial for its
activity, and Raney Nickel doesn’t behave the same once it’s been completely removed.
To be honest I plead ignorance on exactly how Raney nickel works its desulfurizing
magic, although the catalytic hydrogenation process is likely similar to those of Pd/C and
Pt/C.
Real life tips: Perhaps a better description for Raney nickel is “Raney Mud”, because
that’s what it looks and feels like. Raney nickel resembles a kind of mud or wet clay, and
is actually stored in water. Determining the exact molar ratio of Raney nickel to use is
also something of an art – rather than “moles”, typical procedures call for “teaspoons”
[I’m not sure I’m aware of any other reagent that calls for this unit of measurement!] After
dispensing (but before placing in the reaction vessel) the metal is then rinsed with water
(to remove aluminum salts and ensure neutral pH). This can be something of a dicey
prodedure since Raney nickel will spontaneously combust in air when traces of moisture
are removed. Excess Raney nickel on benchtops, spatulas, weighing paper, etc. should
be (carefully) destroyed with acid. There’s nothing like setting up your reaction and then,
out of the corner of your eye, noticing little flames coming from traces of Raney nickel on
your weighing paper. Disclaimer: this paragraph should not suffice as training in the use
of this reagent, which can be extremely dangerous in the wrong hands.