Isolation and Characterization of a Bismuth(II) Radical. Issue 36 (27th July 2015)

• Record Type: Journal Article
• Authors: Schwamm, Ryan J.; Harmer, Jeffrey R.; Lein, Matthias; Fitchett, Christopher M.; Granville, Simon; Coles, Martyn P.
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 36(2015)
• Page Start: 10630
• Page End: 10633
• Publication Date: 2015-07-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201504632
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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‐<italic>i</italic>Pr₂C₆H₃) 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 &gt;90 % spin density in a p‐type orbital on bismuth.</p> </abstract>