Stability of phosphinidenes—Are they synthetically accessible?

Zoltán Benk, Rainer Streubel, L. Nyulászi

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

The relative stability of different singlet phosphinidenes (R–P) has been investigated by using isodesmic reactions. The energies of these reactions with several R groups were calculated with DFT and ab initio methods at different levels of theory. The best stabilising effect on the phosphinidene centre is exhibited by the R′2C═N-group, resulting in a singlet ground state. The analysis of the electron density in the parent H2C═N–P, indicates a considerable double bond character of the PN bond. Further tuning of the C═N π-bond polarity is possible by variation of the R′ substituents. Using trimethylsilyl substituents or incorporating the carbon atom in a π-withdrawing pentafulvene ring the stabilization and the computed singlet triplet separation increases. The thermodynamics and the kinetics of dimerisation reactions of the most stabilised R′2C═N–P indicates that these compounds are likely synthetic targets.

Original languageEnglish
Pages (from-to)4321-4327
Number of pages7
JournalJournal of the Chemical Society. Dalton Transactions
Issue number36
DOIs
Publication statusPublished - Sep 11 2006

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Dimerization
Discrete Fourier transforms
Ground state
Carrier concentration
Carbon
Stabilization
Tuning
Thermodynamics
Atoms
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Stability of phosphinidenes—Are they synthetically accessible? / Benk, Zoltán; Streubel, Rainer; Nyulászi, L.

In: Journal of the Chemical Society. Dalton Transactions, No. 36, 11.09.2006, p. 4321-4327.

Research output: Contribution to journalArticle

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