title: Isolation and Characterization of a Bismuth(II) Radical.
abstract: More than 80 years after Paneth's report of dimethyl bismuth, the first monomeric Bi(II) radical that is stable in the solid state has been isolated and characterized. Reduction of the diamidobismuth(III) chloride Bi(NON(Ar))Cl (NON(Ar)=[O(SiMe2NAr)2](2-); Ar=2,6-iPr2C6H3) with magnesium affords the Bi(II) radical ˙Bi(NON(Ar)). X-ray crystallographic measurements are consistent with a two-coordinate bismuth in the +2 oxidation state with no short intermolecular contacts, and solid-state SQUID magnetic measurements indicate a paramagnetic compound with a single unpaired electron. EPR and density functional calculations show a metal-centered radical with >90% spin density in a p-type orbital on bismuth.
authors.affiliation: School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington 6012 (New Zealand).
authors.forename: Ryan J
authors.initials: RJ
authors.lastname: Schwamm
authors.affiliation: Centre for Advanced Imaging, University of Queensland, St Lucia, Queensland 4072 (Australia).
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Harmer
authors.affiliation: School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington 6012 (New Zealand).
authors.forename: Matthias
authors.initials: M
authors.lastname: Lein
authors.affiliation: Department of Chemistry, University of Canterbury, Christchurch 8041 (New Zealand).
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Fitchett
authors.affiliation: Robinson Research Institute, Victoria University of Wellington, MacDiarmid Institute of Advanced Materials and Nanotechnology, Lower Hutt 5046 (New Zealand).
authors.forename: Simon
authors.initials: S
authors.lastname: Granville
authors.affiliation: School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington 6012 (New Zealand). martyn.coles@vuw.ac.nz.
authors.forename: Martyn P
authors.initials: MP
authors.lastname: Coles
keywords: EPR; bismuth; main-group elements; paramagnetism; stable radicals