Related Experiment Video
Updated: Mar 16, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Generalized Valence Bond Description of Chalcogen-Nitrogen Compounds. III. Why the NO-OH and NS-OH Bonds Are So
Tyler Y Takeshita1, Thom H Dunning1
1Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
Abstract:
Crabtree et al. recently reported the microwave spectrum of nitrosyl-O-hydroxide (trans-NOOH), an isomer of nitrous acid, and found that this molecule has the longest O-O bond ever observed: 1.9149 Å ± 0.0005 Å. This is in marked contrast to the structure of the valence isoelectronic trans-NSOH molecule, which has a normal NS-OH bond length and strength. Generalized valence bond calculations show that the long bond in trans-NOOH is the result of a weak through-pair interaction that singlet couples the spins of the electrons in singly occupied orbitals on the hydroxyl radical and nitrogen atom, an interaction that is enhanced by the intervening lone pair of the oxygen atom in NO. The NS-OH bond is the result of the formation of a stable recoupled pair bond dyad, which accounts for both its length and strength.
Related Concept Videos
Valence Bond Theory
Valence Bond Theory
Polar Covalent Bonds
Chirality at Nitrogen, Phosphorus, and Sulfur
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
Exceptions to the Octet Rule
Coordination Compounds and Nomenclature

