news & views

such as that provided by Martinez and coworkers, particularly important.

Molecular dynamics (MD) is the method
of choice to simulate the application of force
on molecular systems; those performed in
this study were ab initio MD simulations of
cyclobutene at a very high quantum chemical
level. Simulating the external pulling force
can be done in several ways, and the team
led by Martinez use a constant-force mode,
whereby the force applied to the system
remains constant rather than, for example,
the pulling velocity, which does not. If the
constraints applied are not too extreme, one
would expect to find qualitatively similar
chemistry for the different possible pulling
modes. This means that, even if none of
these idealizations fully captures the complex
situation in an ultrasound experiment, any
one of them can be used.
The simulations carried out by Martinez
and co-workers reproduced the antiWoodwardHoffmann behaviour seen
experimentally in the polymerBCB system.
In addition, with static calculations, they
nicely illustrate the effect of force on the two
possible reaction pathways (conrotatory or
disrotatory). This was done for both transand cis-pulling of CB and the larger BCB
(using a less-costly computational method).
This gives a very intuitive picture: though

both reaction pathway potential energy

barriers are lowered on the application of
force, the barrier for one sense of rotation
is lowered far more than the barrier for the
opposite sense. It should be kept in mind,
however, that the relevant information about
the reaction dynamics is gained from the
more demanding MD simulations. Only on
the basis of such simulations is it possible
to decide if the strained system follows the
pathway defined by the potential energy
curves, or, if at high forces, alternative
reaction pathways become relevant.
Although experiment and theory are
in good agreement for the stress-induced
ring-opening, an explanation in terms
of the motion of orbitals or densities is
still missing. This brings us back to the
question: what really constitutes a failure
of the WoodwardHoffmann rules?
The interpretation of the experiment is
complex for several reasons. First, the lone
pairs of the ester groups might affect the
-system. The influence of heteroatoms on
WoodwardHoffmann behaviour has been
discussed previously 6. Second, as Martinez
and co-workers state, it is also possible that
the stereochemistry induced by cis-pulling
in the sonication experiments is set after
the ring-opening reaction. Experimentally
the stereochemistry is determined by a

DielsAlder addition following the ringopening reaction, and this second reaction
might lead preferably to the E,E-isomer.
In other words, to fully understand the
problem systematically, more calculations
and experiments on similar systems are
needed. In particular, single-molecule
atomic force microscopy experiments
would help to explain the effect of a directed
force on the stereochemistry. Mechanical
manipulation of stereochemistry remains a
great challenge, but recent successes in both
theory and experiment give an impression
of the new opportunities that can now be
offered by mechanostereochemistry.

Irmgard Frank and Jana Friedrichs are at

the Institut fr Physikalische Chemie und
Elektrochemie, Leibniz Universitt Hannover,
Callinstrae 3A, 30167 Hannover, Germany.
e-mail: Irmgard.Frank@theochem.uni-hannover.de
References
1. Woodward, R. B. & Hoffmann, R. J. Am. Chem. Soc.
87, 395397 (1965).
2. Woodward, R. B & Hoffmann, R. Angew. Chem. Int. Ed. Engl.
8, 781853 (1969).
3. Hickenboth, C. R. et al. Nature 446, 423427 (2007).
4. Ong, M. T., Leiding, J., Tao, H., Virshup, A. M. & Martinez, T. J.
J. Am. Chem. Soc. 131, 63776379 (2009).
5. Rief, M. & Grubmueller, H. ChemPhysChem 3, 255261 (2002).
6. Volatron, F., Anh, N. T. & Jean, Y. J. Am. Chem. Soc.
105, 23592364 (1983).

CHEMICAL BONDING

Rethinking carbon
The covalent bonding behaviour of carbon is the mainstay of organic chemistry, but in some compounds carbon
seems to behave more like a metal.

C. Adam Dyker and Guy Bertrand

fter Kekuls formulation of the theory

of chemical structure in the 1850s,
the propensity of carbon to form four
bonds quickly became a doctrine, and the
current understanding of carbon chemistry
is still based on this principle. Moreover,
the education of chemists includes the
differentiation between non-metals, carbon
being the archetypical example, and metals.
The paper by Frstner and colleagues on
page 295 of this issue1 is cause to wonder
whether a shift in this doctrine is occurring.
Does carbon really prefer to be tetravalent?
Can carbon behave as a metal?
Although carbon normally uses its four
valence electrons to make four bonds, stable
neutral compounds featuring a carbon atom
with non-bonding electrons are known
(Fig. 1a). These include radicals, with one

non-bonding electron, and carbenes, carbon

monoxide and isonitriles, which have two
non-bonding electrons. Compounds with
three non-bonding electrons at a single
carbon centre, referred to as carbines, are
reactive intermediates that have been poorly
studied. What about four non-bonding
electrons? Such a configuration can be found
in atomic carbon2, the ultimate low-valence
carbon-centre compound that has been
identified in interstellar space. This shortlived species has a triplet ground state, but
most of the reactions that have been reported
so far involve a metastable singlet excited
state located 30 kcal mol1 higher in energy.
A hallmark of atomic carbon chemistry is the
large amount of energy that it brings, which
allows for a wide variety of chemical reactions
that include insertion into very inert bonds.

NATURE CHEMISTRY | VOL 1 | JULY 2009 | www.nature.com/naturechemistry

2009 Macmillan Publishers Limited. All rights reserved

The high reactivity of the abovementioned non-tetravalent carbon

derivatives reflects their strong tendency
to combine with themselves or other
molecules to become tetravalent. How can
the lowest-valence carbon species, with
four non-bonding electrons, be stabilized
while maintaining the neutrality of the
compound? The answer is to have the four
electrons distributed as two lone pairs
and to fill the resulting empty orbitals by
electron donation from Lewis bases. Indeed,
following early experimental work3,4, it has
recently been established theoretically5 that
carbodiphosphoranes 1 (Fig. 1b) should be
considered as consisting of two phosphine
ligands coordinated to a central carbon
atom, a carbon(0) centre, in which the
valence electrons remain as two orthogonal
265

news & views

a
C

Carbene

Radical

Carbine

Atomic carbon

c
C

Ph

Ph

Ph

Ph
Ph

Ph
L

C
C

N
C

C
N

Figure 1 | Carbon can possess non-bonding electrons and behave as a metal. a, These species are highly
reactive owing to their non-bonding electrons. b, Carbodiphosphorane 1 (Ph, phenyl) features a bent
geometry, and is best described with two phosphine ligands donating to carbon. Even though the four
valence electrons of the central carbon are present as two non-bonding lone pairs, 1 can readily be
isolated. Compound 2 exhibits similar geometry and bonding, despite the fact that a classical, linear,
tetravalent allenic structure is possible. This linear geometry is found in the closely related compound 3,
which displays hidden lone pairs. c, The bonding in this class of compound parallels the ligandmetal
interactions typical in coordination chemistry, that is, donation from ligand (L) to the central atom
(M or C), and concurrent back-donation from M or C to L.

lone pairs that are not engaged in chemical

bonding. This analysis is consistent with
the strongly bent geometry, and the
possibility of double protonation, and even
double metallation, at the central carbon
of 1. These studies inspired the search for
other examples of such compounds, and
theoretical as well as experimental studies
have demonstrated that the atypical bonding
in carbodiphosphoranes is maintained
even when other Lewis bases replace the
phosphine moieties. Especially striking is
the use of singlet carbenes68, because the
representation of 2 (Fig. 1b) implies that
even when carbon could be tetravalent, as
expected for an allene, it might prefer to
keep its four electrons as two lone pairs.
Moreover, it has even been suggested1,5 that
compounds such as tetrakis(dimethylamino)
allene 3 (Fig. 1b), which has a classical linear
geometry but a reactivity analogous to that
of carbodiphosphorane 1 and bent allene 2,
displays hidden lone pairs1,9. Frstner and
colleagues1 add that the bonding in 3, and
related compounds, is still best described by
the captodative formalism, that is, donation
from the ligands (L) to the central carbon,
and back-donation of the lone pairs of the
carbon(0) to L, exactly as in metal complexes
(Fig. 1c). They conclude that carbon is
266

capable of serving as the central atom of a

complex just as a metal can do.
Interestingly, the metal-like behaviour
of carbon is not restricted to carbon(0).
Recent results tend to demonstrate that
stable singlet carbenes, with their lone pair
of electrons and accessible vacant orbital,
can do some of the tasks that are typically
reserved for transition metals. The latter are
well known for stabilizing highly reactive
species, and carbenes have recently been
shown to do the same. For example, it has
been reported that N-heterocyclic carbenes
can stabilize a naked Si2 fragment 10. This
species features a siliconsilicon double
bond and, at the same time, a lone pair
of electrons at each silicon, two attributes
that usually confer extreme instability.
Transition metals are able to activate a
variety of small molecules, and similarly it
has been shown that some singlet carbenes
can activate CO (ref. 11), H2 or even NH3
(ref. 12), which is a difficult task for metals.
Even more strikingly, a recent paper has
shown that an N-heterocyclic carbene is
much more efficient than transition-metal
catalysts in achieving reduction of carbon
dioxide to methanol13.
Although the analogy between the
chemistry of metals and the above-mentioned

carbon compounds is striking, it is worth

noting that carbenes are most often used in
conjunction with metals. In fact, carbenes are
now the ligand of choice for preparing highly
active transition-metal catalysts, because
of their strong -donor, weak -acceptor
properties, in combination with the strong
carbonmetal bonds. The ligand properties
of carbon(0) compounds could become just
as important. Indeed, it has already been
predicted that 1 should lead to highly active
olefin-metathesis catalysts14, and it has been
demonstrated that bent allene 2 and its cyclic
versions are stronger donor ligands than
carbenes15. Additionally, whereas carbenes
have only one lone pair of electrons, and can
therefore only bind to one metal, carbon(0)
compounds can use both of their lone pairs to
geminally coordinate to two-metal centres1.
The metal fragments should not need to be
identical, and this opens up the possibility
of chiral coordination complexes. There is
great potential for development in this area,
and carbon(0) compounds could become the
ligands of the future.
Judging from the paper by Frstner and
colleagues1, as well as other recent findings,
the concepts ingrained in organic chemists
throughout their chemical education seem
to face a serious challenge. Hopefully this
will encourage chemists to look beyond
their long-standing beliefs, allowing for new
chemistry and applications for carbon, the
basic element for all known life.

C. Adam Dyker and Guy Bertrand are in the UCRCNRS Joint Research Chemistry Laboratory (UMI
2957), Department of Chemistry, University of
California, Riverside, California 92521-0403, USA.
e-mail: cadamd@ucr.edu; gbertran@mail.ucr.edu
References
1. Alcarazo, M., Lehman, C. W., Anoop, A., Thiel, W. & Frstner, A.
Nature Chem. 1, 295301 (2009).
2. Shevlin, P. B. in Reactive Intermediate Chemistry (eds Moss, R. A.,
Platz, M. S. & Jones, M. Jr) 463500 (Wiley, 2004).
3. Ramirez, F., Desai, N. B., Hansen, B. & McKelvie, N. J. Am. Chem.
Soc. 83, 35393540 (1961).
4. Schmidbaur, H. Angew. Chem. Int. Edn Engl. 22, 907927 (1983).
5. Tonner, R., xler, F., Neumller, B., Petz, W. & Frenking, G.
Angew. Chem. Int. Ed. 45, 80388042 (2006).
6. Tonner, R. & Frenking, G. Angew. Chem. Int. Ed.
46, 86958698 (2007).
7. Dyker, C. A., Lavallo, V., Donnadieu, B. & Bertrand, G.
Angew. Chem. Int. Ed. 47, 32063209 (2008).
8. Frstner, A., Alcarazo, M., Goddard, R. & Lehmann, C. W.
Angew. Chem. Int. Ed. 47, 32103214 (2008).
9. Frenking, G. & Tonner, R. Pure Appl. Chem. 81, 597614 (2009).
10. Wang, Y. et al. Science 321, 10691071 (2008).
11. Lavallo, V., Canac, Y., Donnadieu, B., Schoeller, W. W. & Bertrand,
G. Angew. Chem. Int. Ed. 45, 34883491 (2006).
12. Frey, G. D., Lavallo, V., Donnadieu, B., Schoeller, W. W. &
Bertrand, G. Science 316, 439441 (2007).
13. Riduan, S. N., Zhang, Y. & Ying, J. Y. Angew. Chem. Int. Ed.
48, 33223325 (2009).
14. Tonner, R. & Frenking, G. Chem. Commun. 15841586 (2008).
15. Lavallo, V., Dyker, C. A., Donnadieu, B. & Bertrand, G.
Angew. Chem. Int. Ed. 47, 54115414 (2008).

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2009 Macmillan Publishers Limited. All rights reserved

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