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.
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.
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.
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
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