Gesellschaft Deutscher Chemiker
Keine Benachrichtigungen
Sie haben noch keine Lesezeichen
Abmelden

Artikel

Gas‐Phase Characterization of Hypervalent Carbon Compounds Bearing 7‐6‐7‐Ring Skeleton: Penta‐ versus Tetra‐Coordinate Isomers

Von Wiley-VCH zur Verfügung gestellt

Hypervalent penta-coordinate carbon compounds were characterized by gas-phase techniques, including photodissociation spectroscopy and ion mobility-mass spectrometry. For a compound with moderate electron-donating ligands bearing p-methylthiophenyl substituents, coexistence of penta- and tetra-coordinate forms was revealed, highlighting the significant effects of the environments on the stability of hypervalent carbons.


Abstract

In this study, we afford explicit characterizations of the electronic and geometrical structures of recently reported hypervalent penta-coordinate carbon compounds by using gas-phase characterization techniques: photodissociation spectroscopy (PDS) and ion mobility-mass spectrometry (IM–MS). In particular for a compound with moderately electron-donating ligands, bearing p-methylthiophenyl substituents, the coexistence of tetra- and penta-coordinate isomers is confirmed, consistent with solution characterizations. It is in sharp contrast to the exclusive tetra-coordinate form (with normal valence of the central carbon atom) in the single crystal. This suggests that a non-polar environment makes the penta-coordinate structure thermodynamically most stable. This delicate difference between the tetra- and penta-coordinate structures, which depends on the environment, is a close reflection of the lower activation barrier of the SN2 reaction found in neutral solvent or gas-phase reactions.

Zum Volltext

Überprüfung Ihres Anmeldestatus ...

Wenn Sie ein registrierter Benutzer sind, zeigen wir in Kürze den vollständigen Artikel.