Article

Theoretical Investigations on Chalcogen−Chalcogen Interactions: What Makes These Nonbonded Interactions Bonding?

Christian BleiholderContribution from the Organisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany, Deutsches Krebsforschungszentrum (DKFZ), Im Neuenheimer Feld 280, D-69120 Heidelberg, Germany, Laboratorium für Organische Chemie, Wolfgang-Pauli-Strasse 10, Swiss Federal Institute of Technology Zürich, ETH-Hönggerberg, HCI F 306, CH-8093 Zürich, Switzerland, and Physikalisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, GermanyDaniel B. WerzContribution from the Organisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany, Deutsches Krebsforschungszentrum (DKFZ), Im Neuenheimer Feld 280, D-69120 Heidelberg, Germany, Laboratorium für Organische Chemie, Wolfgang-Pauli-Strasse 10, Swiss Federal Institute of Technology Zürich, ETH-Hönggerberg, HCI F 306, CH-8093 Zürich, Switzerland, and Physikalisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, GermanyHorst KöppelContribution from the Organisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany, Deutsches Krebsforschungszentrum (DKFZ), Im Neuenheimer Feld 280, D-69120 Heidelberg, Germany, Laboratorium für Organische Chemie, Wolfgang-Pauli-Strasse 10, Swiss Federal Institute of Technology Zürich, ETH-Hönggerberg, HCI F 306, CH-8093 Zürich, Switzerland, and Physikalisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, GermanyRolf GleiterContribution from the Organisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany, Deutsches Krebsforschungszentrum (DKFZ), Im Neuenheimer Feld 280, D-69120 Heidelberg, Germany, Laboratorium für Organische Chemie, Wolfgang-Pauli-Strasse 10, Swiss Federal Institute of Technology Zürich, ETH-Hönggerberg, HCI F 306, CH-8093 Zürich, Switzerland, and Physikalisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany

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ABI

Abstract

To understand the intermolecular interactions between chalcogen centers (O, S, Se, Te), quantum chemical calculations on pairs of model systems were carried out. For the oxygen derivatives, one of the components of the supermolecules consists of dimethyl ether, while the second component is either dimethyl ether (1) or ethynyl methyl ether (2) or methyl cyanate (3). The model calculations were also extended to the sulfur (4-6), selenium (7-9), and tellurium congeners (10-12). The MP2/SDB-cc-pVTZ, 6-311G level of theory was used to derive the geometrical parameters and the global energies of the model systems. A detailed analysis based on symmetry adapted perturbation theory (SAPT) reveals that induction and dispersion forces contribute to the bonding in each case. For 1-3 the electrostatic energy also contributes to the intermolecular bonding, but not for 4-12. The NBO analysis reveals that the interaction in the dimers 1-3 is mainly due to weak hydrogen bonding between methyl groups and chalcogen centers. Similar hydrogen bonding is also found in the case of 4 and to a lesser extent in 5 and 7. For the aggregates with heavier centers the chalcogen-chalcogen interaction dominates, and hydrogen bonding only plays a minor role. Electron-withdrawing groups on the chalcogen centers increase the interaction energy and reduce the intermolecular distance dramatically. The one-electron picture of an interaction between the lone pair of the donor and the chalcogen carbon sigma orbital allows a qualitatively correct reproduction of the observed trend.

Identifiers

DOI: 10.1021/ja056827g

Citations and references

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