title: Stable GaX2, InX2 and TlX2 radicals.
abstract: The chemistry of the Group 13 metals is dominated by the +1 and +3 oxidation states, and simple monomeric M(II) species are typically short-lived, highly reactive species. Here we report the first thermally robust monomeric MX2 radicals of gallium, indium and thallium. By making use of sterically demanding boryl substituents, compounds of the type M(II)(boryl)2 (M = Ga, In, Tl) can be synthesized. These decompose above 130 °C and are amenable to structural characterization in the solid state by X-ray crystallography. Electron paramagnetic resonance and computational studies reveal a dominant metal-centred character for all three radicals (>70% spin density at the metal). M(II) species have been invoked as key short-lived intermediates in well-known electron-transfer processes; consistently, the chemical behaviour of these novel isolated species reveals facile one-electron shuttling processes at the metal centre.
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Andrey V
authors.initials: AV
authors.lastname: Protchenko
authors.affiliation: School of Chemistry, PO Box 23, Monash University, Melbourne, Victoria 3800, Australia.
authors.forename: Deepak
authors.initials: D
authors.lastname: Dange
authors.affiliation: 1] Centre for Advanced Electron Spin Resonance, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR [2] Center for Advanced Imaging, University of Queensland, St Lucia, Queensland 4072, Australia.
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Harmer
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Christina Y
authors.initials: CY
authors.lastname: Tang
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Schwarz
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Kelly
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Nicholas
authors.initials: N
authors.lastname: Phillips
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Remi
authors.initials: R
authors.lastname: Tirfoin
authors.affiliation: Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London WC1H 0AJ, UK.
authors.forename: Krishna Hassomal
authors.initials: KH
authors.lastname: Birjkumar
authors.affiliation: School of Chemistry, PO Box 23, Monash University, Melbourne, Victoria 3800, Australia.
authors.forename: Cameron
authors.initials: C
authors.lastname: Jones
authors.affiliation: Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London WC1H 0AJ, UK.
authors.forename: Nikolas
authors.initials: N
authors.lastname: Kaltsoyannis
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Philip
authors.initials: P
authors.lastname: Mountford
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Simon
authors.initials: S
authors.lastname: Aldridge