Title

Effects of Multiple Substitution upon the P∙∙∙N Noncovalent Interaction

Document Type

Article

Journal/Book Title

Chem. Phys.

Publication Date

1-1-2011

Volume

387

First Page

79

Last Page

84

DOI

10.1016/j.chemphys.2011.06.040

Abstract

The attractive noncovalent interaction of a P atom with N is derived primarily from two sources. Charge transfer from the N lone pair into the σ∗ antibonding orbital of a P–X bond that is turned away from the N atom combines with attractive Coulombic forces. As in the case of H-bonding, which is parallel in some ways to P⋯N attraction, placement of an electron-withdrawing substituent on the P atom enhances both of these components, and strengthens the overall interaction. However, in stark contrast with H-bonding, halogenation beyond monosubstitution does not lead to any further strengthening of the P⋯N noncovalent bond. Indeed, di and tri-substitution lead to small reductions in the interaction energy. In all cases, the geometry which contains a P⋯N bond is more stable than other candidate structures, some of which contain hydrogen or halogen bonds.

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