Volume 96 Issue 11 | p. 11 | News of The Week
Issue Date: March 12, 2018 | Web Date: March 8, 2018

Chemists break record for longest C–C bond

New compound contains a 1.806-Å-long alkane bond that stretches beyond theoretical limit
By Tien Nguyen
Department: Science & Technology
News Channels: Organic SCENE
Keywords: Synthesis, longest alkane, hydrocarbon, dihydropyracylene, scissor effect
In two steps, chemists synthesized a compound with the longest reported C–C bond.
Reaction scheme showing the two-step synthesis of a dihydropyracylene compound containing the longest reported C–C single bond.
In two steps, chemists synthesized a compound with the longest reported C–C bond.

The single carbon-carbon bond is among the most familiar covalent connections in organic compounds. But a new study suggests that chemists have yet to fully explore the limits of this basic bond.

Scientists have previously found that these ubiquitous bonds, which typically measure about 1.54 Å in length, can be elongated through the use of bulky substituents to endow molecules with special properties. Now, researchers led by Takanori Suzuki and Yusuke Ishigaki at Hokkaido University have synthesized a molecule with the longest reported C–C bond, measuring 1.806 Å in length (Chem 2018, DOI: 10.1016/j.chempr.2018.01.011).

The team set out to break the record by designing a stable dihydropyracylene compound with a highly strained core and two spirocyclic units that are forced to face each other, helping stretch out the central carbon-carbon bond. The chemists confirmed the presence of the C–C bond by observing its stretching vibration through Raman spectroscopy, and they measured the molecule’s record bond length using X-ray crystallography.

The bond breaks the theoretical limit of 1.803 Å for alkane bond length, previously calculated for caged dimer compounds. This limit is set at the point at which the bond has a dissociation energy of zero and would thus dissociate. Chemists calculated the limit by assuming a linear relationship between bond length and bond dissociation energy. The Hokkaido researchers suggest that molecules like theirs with extralong bonds may deviate from this linear relationship.

Structures with extremely long or short bonds help us refine our understanding of chemical bonding, Peter R. Schreiner of Justus Liebig University Giessen says. He thinks work like this, which pushes the limits of bonding, is worth careful consideration. “It also urges us to keep asking the question, When is a bond a bond?”

Chemical & Engineering News
ISSN 0009-2347
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Stanton de Riel (March 14, 2018 8:13 PM)
It seems that they imagined a strain which would strain the imagination?
S. N. Balasubrahmanyam (March 15, 2018 2:42 AM)
How does zinc do its job? I stretched whatever imagination I have to the Hooke Law limit but I "broke down". can you supply me with a mechanism? Does zinc supply mere electrons while standing aside? Not having access, I haven't read the Suzuki-Ishigaki paper.
Raji Heyrovska (March 15, 2018 12:50 PM)
The various radii of carbon have been related to the Bohr radius (0.639 Å) obtained from the first ionization potential of carbon in: http://arxiv.org/ftp/arxiv/papers/0809/0809.1957.pdf . The radius corresponding to the newly found long CC distance, R(C,long) = d(CC)/2 = 1.806/2 = 0.903 Å = 1.414*0.639, the diagonal of a square with Bohr radius as a side.
Paul Krebaum (March 17, 2018 9:25 PM)
Could the fact that each of the carbon atoms involved is "triply benzylic" have anything to do with it ?
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