Bismuth(III) Complex of the [S4]•- Radical Anion: Dimer Formation via Pancake Bonds

Ryan J Schwamm; Matthias Lein; Martyn P Coles; Christopher M Fitchett

doi:10.1021/jacs.7b10454

Bismuth(III) Complex of the [S₄]^•- Radical Anion: Dimer Formation via Pancake Bonds

J Am Chem Soc. 2017 Nov 22;139(46):16490-16493. doi: 10.1021/jacs.7b10454. Epub 2017 Nov 7.

Authors

Ryan J Schwamm¹, Matthias Lein¹, Martyn P Coles¹, Christopher M Fitchett²

Affiliations

¹ School of Chemical and Physical Sciences, Victoria University of Wellington , P.O. Box 600, Wellington, New Zealand.
² Department of Chemistry, University of Canterbury , Christchurch 8041, New Zealand.

PMID: 29083922
DOI: 10.1021/jacs.7b10454

Abstract

Reaction of bismuth(II) compounds with sulfur gives mixtures of [Bi(NON^R)]₂(μ₂-S_n) (NON^R = [O(SiMe₂NR)₂]^2-). Examples for n = 1 and 3 have been crystallographically verified for R = 2,6-iPr₂C₆H₃ (Dipp) and R = tBu, and the pentasulfide (n = 5) for R = Dipp. The corresponding product from reaction with the new Bi(II) radical Bi(NON^Ar‡)^• (Ar^‡ = C₆H₂(CHPh₂)₂-tBu-2,6,4) exists as the dimer [Bi(NON^Ar‡)(S₄)]₂, with π*(SOMO)-π*(SOMO) interactions linking the sulfur chains through trans-antarafacial pancake bonds.