Oxidative bond formation and reductive bond cleavage at main group metal centers: reactivity of five-valence-electron MX₂ radicals

Andrey V Protchenko; Deepak Dange; Matthew P Blake; Andrew D Schwarz; Cameron Jones; Philip Mountford; Simon Aldridge

doi:10.1021/ja5062467

Oxidative bond formation and reductive bond cleavage at main group metal centers: reactivity of five-valence-electron MX₂ radicals

J Am Chem Soc. 2014 Aug 6;136(31):10902-5. doi: 10.1021/ja5062467. Epub 2014 Jul 28.

Authors

Andrey V Protchenko¹, Deepak Dange, Matthew P Blake, Andrew D Schwarz, Cameron Jones, Philip Mountford, Simon Aldridge

Affiliation

¹ Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.

PMID: 25036798
DOI: 10.1021/ja5062467

Abstract

Monomeric five-valence-electron bis(boryl) complexes of gallium, indium, and thallium undergo oxidative M-C bond formation with 2,3-dimethylbutadiene, in a manner consistent with both the redox properties expected for M(II) species and with metal-centered radical character. The weaker nature of the M-C bond for the heavier two elements leads to the observation of reversibility in M-C bond formation (for indium) and to the isolation of products resulting from subsequent B-C reductive elimination (for both indium and thallium).