Markup Help 
All posts Reviews Conferences Research

In the special issue 90 Years of Chemical Bonding1 I expressed the opinion2 that despite of the historians characterization of chemistry as a science without territory, the chemical bond has been the traditional chemical territory and the heartland of chemistry ever since the chemical community amalgamated in the 17th Century.  While historians seem to ignore this chemical territory, the good news is that chemists have kept it fertile and teaming with activity, generating new bonding motifs and news (see for example, the recent highlight in CCH, April 4, 2012). One of the recent new and exciting bonding motifs, was found by Peter R. Schreiner and his group3 who have synthesized molecules with very long C-C bonds, 1.647-1.704 by Wurtz coupling of so-called diamondoid molecules (nanodiamonds), e.g., 1 which results from diamantane-diamantane coupling.  

                        1                                                                                                    2
Schreiner et al.3 used also DFT calculations to show that ~ 40% of the bond dissociation energy (BDE) of these long C-C bonds is due to the dispersion interactions, and argued that the sticky dispersion interactions are due to short H---H contacts (1.94 and 2.28 ) that are maintained between the CH---HC faces of the diamondoid moieties.
In a subsequent study, which is described in the highlighted paper,4 Stefan Grimme and Peter R. Schreiner teamed to solve the riddles exhibited by hexaarylethanes.  The parent molecule, hexaphenylethane, is experimentally unknown as it dissociates readily into two Gomberg radicals, 2Ph3C. Similarly, hexa-(para-tert-butylphenyl)-ethane dissociates into its corresponding radicals. By contrast, the apparently much more crowded hexa-(3,5-di-tert-butylphenyl)ethane (2) is a stable molecule with a very long C-C bond of 1.67 . Structure 2is the only one that maintains attractive H---H interactions between the meta-di-substituted phenyl groups. Grimme and Schreiner showed that in all the hexaarylethanes, the BDE is negative in the absence of dispersion interactions, but becomes positive upon addition of dispersion. However, only 2 has a positive dissociation free energy. Furthermore, computational removal of the dispersion contributions of the tert-butyl groups would have made 2 unstable with BDE<0. Therefore, the sticky fingers that hold the C-C bond in 2 are the H---H interactions, which contribute 40 kcal/mol to the total BDE (>50%). These sticky fingers create a second minimum in the bond dissociation energy curve of 2. This minimum, so-called 2vdw, lies at a C-C distance of ~5.2 and its binding energy is purely dispersive and amounts to 26.6 kcal/mol. That is, 2vdwis held exclusively by the sticky H---H fingers!
The role of the sticky H---H fingers was subsequently probed by Fokin, Schreiner et al., to stick together layers of graphanes.5The potential practical applications of these dispersion-supported bonds are wide ranging. There is something new and potable in chemical bonding!
(1) G. Frenking, S. Shaik, 90 Years of Chemical Bonding, J. Comput. Chem. 2007, 28, 1-455.
(2) S. Shaik, The Lewis Legacy: The Chemical Bond-A Territory and Heartland of Chemistry, J. Comput. Chem. 2007, 28, 51-61.
(3) P. R. Schreiner, L. V. Chernish, P. A. Gunchenko, E. Y. Tikhonchuk, H. Hausman, M. Serafin, S. Schlecht, J. E. P. Dahl, R. M. K. Carlson, A. A. Fokin, Overcoming Lability of Extremely Long Carbon-Carbon Bonds Through Dispersion Forces, Nature, 2011, 477, 308-312.
(4) S. Grimme, P. R. Schreiner, Steric Crowding Can Stabilize a Labile Molecule: Solving the Hexaphenylethane Riddle:, Angew. Chem. Int. Ed. 2011, 50, 12639-12642.
(5) A. A. Fokin, D. Gerbig, P. R. Schreiner, ss- and p/p-Interactions Are Equally Important: Multilayered Graphanes, J. Am. Chem. Soc. 2011, 133, 20036-20039.

Contributed by Sason Shaik

Posts linking to this one

Computational Chemistry Highlights received nearly 21,000 pageviews in 2012.A total of 62 highlights were published in 2012 and the five most viewed highlights are1. Chemical Networks (Triple Header!) highlighted by Robert Paton in July2. Steric...
The April issue of Computational Chemistry Highlights is out. CCH is an overlay journal that identifies the most important papers in computational and theoretical chemistry published in the last 1-2 years.  CCH is not affiliated with any publisher: it...
Fokin, A. A.; Chernish, L. V.; Gunchenko, P. A.; Tikhonchuk, E. Y.; Hausmann, H.; Serafin, M.; Dahl, J. E. P.; Carlson, R. M. K.; Schreiner, P. R. J. Am. Chem. Soc., 2012, 134, 13641 (Paywall)Contributed by Steven Bachrach.Reposted from Computational Organic...
Schreiner has expanded on his previous paper1 regarding alkanes with very long C-C bonds, which I commented upon in this post. He and his colleagues report2 now a series of additional diamond-like and adamantane-like sterically congested alkanes that are stable...