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(such as 6 in Fig. 1b). Copolymerization observed in the films. It is proposed that References
of these functional monomers produces these groups could be used to provide 1. Marimuthu, M. & Kim, S. Curr. Nanosci. 5, 189–203 (2009).

polymers that can be crosslinked by further functionality by reaction with 2. Place, E. S., George, J. H., Williams, C. K. & Stevens M. M.
Chem. Soc. Rev. 38, 1139–1151 (2009).
dimerization of the pendant ketenes. nucleophiles as described above.
3. Perlin, L., MacNeil, S. & Rimmer, S. Soft Matter
Of course, the main motivation for This research undoubtedly has 4, 2331–2349 (2008).
producing functional polymers is the potential as a versatile way of introducing 4. Jagur-Grodzinski, J. Polym. Adv. Technol. 21, 27–47 (2010).
production of new technologies. One both crosslinking and functionality for 5. Dhal, P. K., Polomoscanik, S. C., Avila, L. Z.,
example of how this method might be used polymeric materials as part of a post- Holmes-Farley, S. R. & Miller, R. J. Adv. Drug Deliv. Rev.
is demonstrated through the formation synthetic modification strategy, provided the 61, 1121–1130 (2009).
of patterned thin films (see Fig. 1c). The application of interest can tolerate the high 6. Ghanbari, H. et al. Trends Biotechnol. 27, 359–367 (2009).
7. Leibfarth, F. A. et al. Nature Chem. 2, 207–212 (2010).
polymers proved to be stable and did not temperature of the pyrolysis process and the
8. Meldrum, A. N. J. Chem. Soc. 93, 598–601 (1908).
crosslink under ambient conditions until release of volatile by-products. ❐
9. Moad, G. & Solomon, D. H. The Chemistry of Radical
the ketene was unmasked by pyrolysis of Polymerization (Elsevier, 2005).
the Meldrum’s acid functionality. Perhaps Steve Rimmer is in the Polymer Centre, Department 10. Kosravi, E. & Szymanska-Buzar, T. (eds) Ring Opening Metathesis
surprisingly — given the reactivity of of Chemistry at the University of Sheffield, Sheffield, Polymerisation and Related Chemistry: State of the Art and Visions
ketenes — residual ketene groups were S3 7HF, UK. e‑mail: s.rimmer@sheffield.ac.uk for the New Century (Kluwer Academic, 2002).

ISOMERISM

The same but different


Electromerism is an unfamiliar concept to many chemists and refers to molecules that are not conventional isomers
but instead differ in how the electrons are distributed across their structure. A novel example of such electromers
has now been demonstrated.

Thomas Bally

I
somerism is a central concept in Electromers of the same multiplicity cationic form, which is stable if paired
chemistry and all who study this branch are most often encountered in transition with the very non-nucleophilic B[3,5-
of science learn that molecules of the same metal complexes carrying ligands that (CF3)2C6H3]4– (‘BARF’) anion. On one-
elemental composition may differ in the can exist in different oxidation states, electron reduction using elemental
way their constituent atoms are connected such as the phenoxy/phenolate or sodium, sodium naphthalenide or CoCp*2
by chemical bonds (constitutional isomers) the quinone/semiquinone/catechol (Cp* = pentamethylcyclopentadienyl),
or in the spatial arrangement of the groups1. In some such cases, equilibria two distinct radicals were formed that
chemical bonds (stereoisomers). The latter between distinct electromers of the form Grützmacher, de Bruin and co-workers
class can also be subdivided to distinguish Mz(Lny) Mz–e(Lnz+e) (where z, y and e named L˙ and M˙. The two species were
diastereomers (for example, cis–trans- or refer to charges) can be observed to shift fully characterized by different forms of
E–Z-isomers, conformers or rotamers) from on photolysis, or on changing external electron paramagnetic resonance (EPR)
molecules that are mirror images of each parameters such as temperature or spectroscopy, and the L˙ M˙ equilibrium
other (enantiomers). pressure (if e > 1, the e electrons may be could be reversibly shifted from 66% of L˙ at
Another, less familiar class of isomers transferred to n different ligand molecules). 340 K to 88% of L˙ at 190 K.
are ‘electro-isomers’ (known also by their Unfortunately, such electromers have To understand the structure of the
short name, electromers). These are pairs recently been named ‘valence tautomers’1, radicals, density functional theory (DFT)
of molecules that do not differ in their which can lead to some confusion because calculations were carried out that revealed
constitution, nor much in the spatial in organic chemistry the term ‘tautomer’ two distinct potential energy minima
disposition of the bonds between the is reserved for isomers that differ in their within approximately 2 kcal mol–1, L˙calc
atoms, but solely in the way the electrons bonding pattern to hydrogen. and M˙calc (in addition to a third one, L˙′calc,
are distributed amongst the atoms and the There are, however, some cases where which, however, differs from L˙calc only by
bonds that link them. electromerism is of a more subtle nature. rotation around the Rh–P2Ph3 bond). Apart
The most obvious class of electromers Now writing in Angewandte Chemie from the Rh–P2Ph3 bond length which is
are excited electronic states, but as those International Edition, Grützmacher, de 0.047 Å longer in L˙calc the two isomers
have usually only a very fleeting existence, Bruin and colleagues present an intriguing have very similar bond lengths, but M˙calc
they cannot be put on an equal footing with organometallic case in which the electromers distinguishes itself by having a much smaller
different stable ground-state structures. In do not require redox-active ligands2. P1–Rh–P2 angle, which gives it a structure
principle, states of different multiplicity They studied a rhodium complex similar to a trigonal bipyramidal complex
such as those that occur in spin crossover carrying bis(dibenzotropyl)phosphine such as is observed when the P1Ph moiety
compounds for example, may be regarded (where the phosphorous atom is denoted is replaced by the more electron-donating
as electromers, but in that research field the P1) and triphenylphospine (P2) ligands SiMe group (Fig. 1a).
term ‘spin isomerism’ is used to describe with the arrangement shown in Fig. 1a. The differences in the electronic structure
such species. The complex was first prepared in its of L˙ and M˙ express themselves most clearly

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a As electronic reorganizations are



Ph
• inherently barrierless, the barrier that
P1 Ph
P1 P1
Ph separates M˙ from L˙ must arise because
BARF – Reduction + the ground state of M˙ correlates with an
122.0°
Rh Rh 165.5°
Rh excited state of L˙ along the deformation
P2Ph3 that leads from the structure of M˙ to the
P2Ph3 P2Ph3
structure of L˙, and vice versa. Indeed, it
L• M• would be interesting to know where the
electronic state of L˙, which corresponds
to the electronic structure of M˙, lies and
P1
Ph vice versa, but Grützmacher, de Bruin and
P1Ph = co-workers do not give any information on
that. The rhodium complex described does,
however, demonstrate that electromerism in
organometallic chemisty is not restricted to
complexes carrying redox-active ligands. It
can occur in cases where an unpaired electron
b occupies one or another orbital of a complex,
provided that there is a suitable distortion
that stabilizes the ‘excited state’ to the extent
that it becomes an isomeric ground state.
This situation is reminiscent of the one
that prevails in the open-shell compounds
that are subjected to Jahn–Teller distortion,
except that in those cases, only one of
Ph the ‘electromers’ usually corresponds to
Ph a potential energy minimum, whereas
Ph
Ph Ph the other is a transition state for its
Ph automerization3. In recent research4 we have
L• M• observed a case of true electromerism in a
pair of organic radical cations containing
Figure 1 | Electromerism in an organometallic compound. a. Formation and structures of radicals L• and two allylic moieties. The two electromers
M•. The benzo rings that are annellated to the tropyl ligands are omitted for clarity and replaced with red distinguish themselves by the nature of the
double bonds. b. The different spin densities (shown in blue) of the electromeric radicals L• and M•. Part b singly occupied MO (SOMO), which in
reproduced with permission from ref. 2, © Wiley 2010. one case corresponds to the positive, and
in the other to the negative combination
of the constituent allylic SOMOs. This
in their EPR spectra, especially the difference than half of that on the rhodium atom) example shows that the phenomenon of
in the hyperfine coupling constants to the 31P1 — see Fig. 1b. This leads Grützmacher, de electromerism is not bound to the presence
atom in Fig. 1a (Aiso = 53 MHz for L˙ versus Bruin and co-workers to describe L˙ as a of transition metals — and, as Grützmacher,
602 MHz for M˙) and, to a lesser degree, in “strongly delocalized organometallic radical” de Bruin and co-workers have shown, to
that to the103Rh atom (Aiso = 10 MHz for L˙ whereas they consider M˙ as a “metallo redox-active ligands — and thus it may be
versus 3 MHz for M˙). The DFT calculations radical with a high localization of spin in the more prevalent throughout chemistry than
show, however, that the changes in Aiso do Rh–P1 bond”. we might think. ❐
not translate directly into changes in spin In a molecular orbital (MO) picture,
density on these atoms, presumably due to the odd electron in L˙ occupies an Thomas Bally is in the Department of Chemistry,
the changes in hybridization at the rhodium MO that is localized mostly on the two University of Fribourg, Pérolles, CH‑1700 Fribourg,
atom: although the calculated spin density P1-(dibenzotropyl) ligands, whereas in Switzerland. e‑mail: Thomas.Bally@unifr.ch
on the P1 atom increases from 12% to 28% M˙ it resides in an MO that is localized
on going from L˙ to M˙, so does that on mostly on the Rh- and the P1-atom. With References
rhodium (from 33 to 58%). this perspective, M˙ can be regarded as 1. Evangelista, E. & Ruiz-Molina, D. Eur. J. Inorg. Chem. 2005,

More importantly, spin density shifts a low-lying excited state of L˙ that gains 2957–2971 (2005).
2. Puschmann, F. F. et al. Angew. Chem. Int. Ed. 49, 385–389 (2010).
from the hydrocarbon parts of the ligands a spectroscopically palpable existence 3. Herzberg, G. Electronic Spectra and Electric Structure of
— which carry 46% of the spin in L˙ — to by virtue of a barrier (calculated as Polyatomic Molecules (Krieger, 1991).
the central P1–Rh–P2 moiety, which carries approximately 3 kcal mol–1) that separates it 4. Müller, B., Bally, T., Gerson, F., de Meijere, A. & von Seebach, M.
nearly 90% of the spin in M˙ (with more from its ‘electronic isomer’ L˙. J. Am. Chem. Soc. 125, 13376–13783 (2003).

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