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Transmission of electronic substituent effects through cage polycyclic alkanes: a computational study of diamantane derivatives based on structural variation

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Abstract

The transmission of long-range polar effects (field effects) across the diamantane cage has been investigated by analyzing the small structural changes induced by a variable substituent X in the phenyl group of 9-substituted 4-phenyldiamantane derivatives. The structures of many such molecules with charged or dipolar substituents have been determined from quantum chemical calculations at the HF/6-31G* and B3LYP/6-311++G** levels of theory. Comparison with the results of a similar study carried out on 4-substituted 1-phenylbicyclo[2.2.2]octane derivatives, where the distance between probe and substituent is substantially smaller, shows that the ability of the diamantane framework to transmit field effects is 45 % of that of the bicyclo[2.2.2]octane framework when X is a dipolar, uncharged substituent. This figure increases to 59 % in the case of charged groups. The structural results support the idea that the field effect of a dipolar substituent attenuates more rapidly with distance than that of a charged group. This makes it impossible to construct a single, universal scale of field parameters including both dipolar and charged groups. A single scale can only be set up for a fixed separation between substituent and probe. The presence of the variable substituent X has a pronounced effect on the geometry of the diamantane cage. The nonbonded distance between the bridgehead carbons C4 and C9 spans an interval about 0.20 Å wide and correlates quite well with the mean value of the three cage angles at C9. These geometric changes are closely similar to those of the corresponding parameters in 4-substituted 1-phenylbicyclo[2.2.2]octane derivatives. The concerted structural variation of the polycyclic cage is controlled primarily by the group electronegativity of X and does not correlate with the much smaller structural variation of the phenyl probe.

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Acknowledgments

This work was supported by the CASPUR Supercomputing Center, Rome, with a Standard HPC Grant 2012 (“A combined X-ray absorption spectroscopy, molecular dynamics simulations, and quantum mechanics calculation procedure for the structural characterization of ill-defined systems”) and by the CINECA Supercomputing Center, Bologna, with Project IsC10_DYNGEO_E.

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Authors and Affiliations

  1. Department of Chemistry, Sapienza – University of Rome, 00185, Rome, Italy

    Anna Rita Campanelli

  2. Department of Physical and Chemical Sciences, University of L’Aquila, 67100, L’Aquila, Italy

    Aldo Domenicano

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  1. Anna Rita Campanelli
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  2. Aldo Domenicano
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Correspondence to Anna Rita Campanelli or Aldo Domenicano.

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Campanelli, A.R., Domenicano, A. Transmission of electronic substituent effects through cage polycyclic alkanes: a computational study of diamantane derivatives based on structural variation. Struct Chem 25, 691–698 (2014). https://doi.org/10.1007/s11224-014-0400-z

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