Sofia Kiriakidou

[Frustrated
Lewis Pairs]

Dealing with the Lewis basicity and acidity is one of the most common methods to understand inorganic
chemistry. For instance, Lewis donor-acceptor interactions can explain the bonding of a base-acid adduct. In
the way of exploring these properties, Stephan et al. posed themselves a question; could steric congestion
induce the result of an adduct formation? The answer was obviously yes, and there is the point where the
Frustrated Lewis Pair (FLP) chemistry steps in.
The FLPs are Lewis pairs which cannot form the classical Lewis acid-base adduct due to steric congestion.
The unquenched Lewis basicity and acidity results into high reactivity with H
2
and other small molecules.
Specifically for hydrogen, they can split it heterolytically, so it forms a hydrid and a proton.
The FLPs is a new, partially discovered, yet very
important part of inorganic chemistry and its
applications. Primarly, they are the first non-transition-
metal system that can take up and release hydrogen.
Furthermore, they can contribute to non-metal
heterogenous catalysis, by the following mechanism:


a proton and a hydrid are transferred from the FLP adduct
(e.g. a phosphonium borate-figure 2) to the substrate, then the
phosphine-borane is regenerated and finally it can be used to
reactivate a new hydrogen molecule, so the cycle is repeated.
All the FLP reactions take place in mild conditions, so they can lead to the saving of energy and money.
The pioneer of this field was H. C. Brown, who commented in 1942 that steric demands can intervene in
the formation of donoracceptor adducts of pyridines with BMe
3
(1). Later on, in 1988, Erket et al. found out
that when the Lewis acid B(C
6
F
5
)
3
and the sterically encumbered ylide, Ph
3
PCHPh are combined, in addition
to the classical adduct (Ph
3
PCHPh)B(C
6
F
5
)
3
, also the species [Ph
3
PCHPh(C
6
F
4
)BF(C
6
F
5
)
2
] was formed, due to
sterical reasons (2).
More recently, in 2009, the researcher of the article being presented, Douglas W. Stephan, proposed a new
strategy to FLP hydrogenation and other small molecule activation (3).



Figure 1. Example of an FLP (6)
Figure 2. Example of H
2
by the phospine-
borane complex
Sofia Kiriakidou
[Frustrated
Lewis Pairs]
The most important findings of this review are described by the following reactions.
SIMPLE PHOSPHINE-BORANE FLP ACTIVATION OF H
2

Sterically hindered phosphines cannot form the classical Lewis acid-base adduct when added to boranes.
However, when they are exposed to H
2
and a pressure of 1 atm, they react immediately the FLP adduct and so
they capture hydrogen, in the form of a hydrid and a proton.
R
3
P + B(C
6
F
5
) [R
3
PH][HB(C
6
F
5
)
3
]
The proposed mechanism can be described by the following picture:



The fluorides of the borane stabilize the structure, but steric
congestion prevents a covalent bond between phosphorus
and borion to form.

CARBENE BASED FLPs
The carbenes present a special edition of FLP because the donor and the acceptor that are sterically hindered
reside on the same atom. The orthogonal relationship between the lone pair and the vacant p-orbital results in
an unquenched Lewis basicity and acidity. For this reason, they can be also used for hydrogen or ammonia
activation, as we can see in the following reactions:

Stephan and co-workers also worked on other small molecules, like olefins and dienes.

As far as new directions in the field are concerned, the research is mostly orientated in finding new
compounds (except phosphines and borane) that can perform such FLP addition, and also new types of small
molecules that can be activated. Furthermore, it is of first importance that the mechanism of catalysis is
further explored and optimized.
G. Erker et al. (4) dealt with the problem of heterogenous catalysis with Pd on charcoal for hydrogenation
to the C=C bond on C3 of a ferrocenophane. The classic metal-based catalysis, ended up in non-selectively
hydrogenating all the double bonds in the ferrocenophane molecule. As a solution an FLP method was used
which resulted in a 77:23 mixture of 1,4 hydrogenated and double hydrogenated, according to the following
mechanism:
Figure 3 Mechanism of FLP hydrogenation
Sofia Kiriakidou
[Frustrated
Lewis Pairs]









Further research is also going on activating alkynes with FLP addition of chloro- and phenoxy-
phosphines, by the group of Douglas W. Stephan et al. (5) The addition could either not be established (due to
sterics or electron withdrawing effect- when it comes to chloro-phosphines) or it ended up in a mixture of the
acid-base adduct and the reactants. The problem was solved when an FLP addition took place, using phenyl
acetylene (PhCCH), as it is shown in the following reactions:
general:

tBu (C
6
H
4
O
2
)P + B(C
6
F
5
)
3
PhCCH

tBu(C
20
H
12
O
2
)P + B(C
6
F
5
)
3


PhCCH


The FLP chemistry has a great potential of developing in the future. It can propose new methods of catalysis
which may totally replace the costly and environmentally harmful metal catalysis and it can also be used for
hydrogen transportation and other small molecules activation. One main disadvantage is that, at least until
now, the FLP method cannot be used for hydrogen storage- which is a current trend in chemistry research-
Sofia Kiriakidou
[Frustrated
Lewis Pairs]
because the requirement of steric congestion is a strong limitation for application in hydrogen storage where
high hydrogen content in mass is required.
Bibliography
1. H. C. Brown, H. I. Schlesinger and S. Z. Cardon. s.l. : J. Am. Chem. Soc., Vols. 1942, 64, 325.
2. S. Doering, G. Erker, R. Frohlich, O. Meyer and K. Bergander. s.l. : Organometallics, 1988, Vols. 17, 2183.
3. A new stratefy to FLP hydrogenation and other small molecule activation. Stephan, D. W. s.l. : Dalton Trans,
2009, Vols. 31293136.
4. Organometallic frustrated Lewis pair chemistry. ErkerG. 7475-7483, s.l. : Dalton Trans., 2011, Vol. 40.
5. Chloro- and phenoxy-phosphines in frustrated Lewis pair additions to alkynes. Christopher B. Caputo, Stephen J.
Geier , Eva Y. Ouyang , Christoph Kreitner and Douglas W. Stephan. 237-242, s.l. : Dalton Trans., 2012, Vol. 41.
6. http://www.columbia.edu/cu/chemistry/ance/stephan/ance.html. [Online]