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

Satoru Muramatsu, Keijiro Ohshimo, Yuan Shi, Motoki Kida, Rong Shang, Yohsuke Yamamoto, Fuminori Misaizu, Yoshiya Inokuchi

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

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.

Original languageEnglish
Article numbere202203163
JournalChemistry - A European Journal
Volume29
Issue number11
DOIs
Publication statusPublished - 2023 Feb 21

Keywords

  • hypervalent compounds
  • ion-mobility mass spectrometry
  • laser spectroscopy
  • photodissociation spectroscopy
  • S2 reaction transition state

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