Spin distributions, ring conformations, and spiroconjugation in "phosphaverdazyl" radicals

Inorganic Chemistry
R G HicksG W Patenaude

Abstract

Reaction of P-dimethylaminophosphonic acid bis(1-methylhydrazide) (6) with trimethyl orthobenzoate gave 1,2,5,6-tetrahydro-1,5-dimethyl-6-(N,N-dimethylamino)-6-phenyl-1,2,4,5,6-tetrazaphosphorine-6-oxide (7), which was subsequently oxidized to the corresponding P-diemthylamino-6-phosphaverdazyl (5) as a persistent radical. Analysis of the electron paramagnetic resonance spectrum of 5 revealed significant spin density on the exocyclic nitrogen but very little spin density on the phosphorus, in contrast to the previously reported P-phenyl-6-phosphaverdazyl (4). Density functional theory calculations on simplified models of 4, 5, and related radicals were performed and revealed that spin polarization effects and the nature of the substituents on phosphorus have significant effects on the structures and spin distributions of these radicals. The spin transfer to the dimethylamino group in 5 was revealed to arise from spiroconjugation-type overlap between the nitrogen 2p orbital with the verdazyl radical singly occupied molecular orbital.

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew

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Citations

Feb 26, 2013·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Linna ZhuChuluo Yang
Apr 28, 2007·Organic & Biomolecular Chemistry·Robin G Hicks
Dec 6, 2019·Chemical Society Reviews·Joe B Gilroy, Edwin Otten
Oct 7, 2010·The Journal of Physical Chemistry. a·Debojit BhattacharyaAnirban Misra

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