Work

Isocyanides Versus Nitriles: Divergent Hydrogen Bonding Behavior Driven by the Balance Between Dispersive and Electrostatic Forces

Year: 2026

Type: article

Abstract: Isocyanides as hydrogen‐bond acceptors are characterized using jet‐cooled Fourier transform infrared spectroscopy for the first time. The hydrogen‐bonded structures of tert ‐butyl isocyanide ( t ‐BuNC) and its constitutional isomer pivalonitrile ( t ‐BuCN) with a single H 2 O or tert ‐butyl alcohol ( t ‐BuOH) molecule are analyzed. The most stable monohydrate structures differ markedly: t ‐BuNC adopts a classical σ ‐type hydrogen bond, whereas t ‐BuCN favors a dispersion‐stabilized orthogonal π ‐type arrangement. Substitution of H 2 O with the more polarizable t ‐BuOH enhances dispersion interaction between the molecules and drives both complexes toward π ‐type binding motifs. These findings highlight the balance between dispersive and electrostatic interactions in governing noncovalent binding preferences.

Source: ChemPhysChem

DOI: 10.1002/cphc.202500834

Authors: Alexander Kanzow, Martin A. Suhm, Margarethe Bödecker

Institution: University of Göttingen

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,550

Funder: Deutsche Forschungsgemeinschaft