Synthesis, Structure, NMR Spectroscopy, and Electrochemistry of the Sterically Congested Triarylarsine Dipp3As: EPR Characterization of its Radical Cation

Mona Taghavikish; Brock L. Price; Tracey L. Roemmele; René T. Boeré

doi:10.1071/CH13244

RESEARCH ARTICLE

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Synthesis, Structure, NMR Spectroscopy, and Electrochemistry of the Sterically Congested Triarylarsine Dipp₃As: EPR Characterization of its Radical Cation

Mona Taghavikish ^A , Brock L. Price ^A , Tracey L. Roemmele ^A and René T. Boeré ^A ^B

+ Author Affiliations

- Author Affiliations

^A Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, Alberta, T1K3M4, Canada.

^B Corresponding author. Email: boere@uleth.ca

Australian Journal of Chemistry 66(10) 1226-1234 https://doi.org/10.1071/CH13244
Submitted: 7 May 2013 Accepted: 11 June 2013 Published: 2 August 2013

Abstract

The synthesis, NMR spectroscopy, single-crystal X-ray structure, and solution electrochemistry of the new compound [2,6-{CH(CH₃)}₂C₆H₃]₃ As, abbreviated as Dipp₃As, is reported. The molecule, prepared by reaction of AsCl₃ with a pre-formed aryl copper reagent, Dipp₄Cu₄, crystallizes in the hexagonal space group R3 as a racemic twin. The sum of angles around As, ∑∠{CAsC}, is 329.13(3)° in the X-ray structure and 329.17° from an R-B3LYP/6-31G(d,p) hybrid density functional theory calculation. The aromatic rings are quite distorted with both the ipso carbon and especially the As atom significantly out of plane by 0.503(3) Å. The ambient temperature NMR spectrum fits for C₃ symmetry implying that inversion is slow on the NMR timescale. Cyclic voltammetry on a glassy carbon electrode in CH₂Cl₂ with 0.4 M [ⁿBu₄N][PF₆] over scan rates of 0.05–0.8 V s^–1 and temperatures of 22 ± 2°C produced one quasi-reversible process with E_m1 = +0.43 V at a scan rate of 0.20 V s^–1 and a second irreversible process with a peak potential of +1.45 V (v. Fc^+/0). The diffusion coefficient has been measured as 3.3 ± 0.1 × 10^–6 cm² s^–1 in CH₂Cl₂ solution containing 0.4 M [ⁿBu₄N][PF₆]. Chemical oxidation with AgPF₆ in CH₂Cl₂ in degassed solutions in sealed vessels allowed for recording of characteristic EPR spectra; at 293 K, a (⁷⁵As) = 26.1 mT and g = 2.021. In frozen solution, an almost isotropic spectrum is obtained (g_║ = 2.000 mT and g_⊥ = 2.003 mT) and the hyperfine splitting constants are a_║ = 47.9 and a_⊥ = 19.0 mT, leading to an estimate for the structure being slightly pyramidal with ∑∠{CAsC} ≈ 351°.

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Synthesis, Structure, NMR Spectroscopy, and Electrochemistry of the Sterically Congested Triarylarsine Dipp3As: EPR Characterization of its Radical Cation

Abstract

References

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Synthesis, Structure, NMR Spectroscopy, and Electrochemistry of the Sterically Congested Triarylarsine Dipp₃As: EPR Characterization of its Radical Cation