Vibronic transitions and spin-orbit coupling of three-membered metallacycles formed by lanthanide-mediated dehydrogenation of dimethylamine

Silver Nyambo, Yuchen Zhang, Dong Sheng Yang

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Metal-mediated N-H and C-H bond activation of aliphatic amines is an effective strategy for synthesizing biologically important molecules. Ln (Ln = La and Ce) atom reactions with dimethylamine are carried out in a pulsed-laser vaporization supersonic molecular beam source. A series of dehydrogenation species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln-containing species in the formula Ln(CH2NCH3) are characterized by single-photon mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and multiconfiguration self-consistent field and quasi-degenerate perturbation theory for the Ce species. The MATI spectrum of La(CH2NCH3) consists of a single vibronic band system, which is assigned to the ionization of the doublet ground state of N-methyl-lanthanaaziridine. The MATI spectrum of Ce(CH2NCH3) displays two vibronic band systems, which are attributed to the ionization of two-pair lowest-energy spin-orbit coupling states of N-methyl-ceraaziridine. Both metallaaziridines are three-membered metallacycles and formed by the thermodynamically and kinetically favorable concerted dehydrogenation of the amino group and one of the methyl groups.

Original languageEnglish
Article number034302
JournalJournal of Chemical Physics
Volume155
Issue number3
DOIs
StatePublished - Jul 21 2021

Bibliographical note

Funding Information:
We gratefully acknowledge financial support from the National Science Foundation Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms, Grant No. 1800316).

Publisher Copyright:
© 2021 Author(s).

ASJC Scopus subject areas

  • Physics and Astronomy (all)
  • Physical and Theoretical Chemistry

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