Heavier Group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates: a structurally characterized monomer-dimer pair for gallium

Andrew Hawley, Andy Ohlin, Lea Fohlmeister, Andreas Stasch

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We have synthesized and characterized the monomeric diiminophosphinate-stabilized Group13 metal(I) complexes [DipLE:], DipL=Ph2P(NDip)2, Dip=2,6-iPr2C6H3; E=Ga (1), In (2) and Tl (3). In addition, we structurally characterized the dimeric complex [(DipLGa)2], 12. Similar synthetic attempts using MesL=Ph2P(NMes)2, Mes=2,4,6-Me3C6H2 afforded product mixtures from which the mixed oxidation state species [(MesL)3Ga4I3] 4 was isolated. [DipLGa:] 1 is converted with dry air to the gallium(III) oxide species [(DipLGaO)2] 5. Density Functional Theory studies on [DipLE:] and [(DipLE)2], E=Al-Tl, shed light on the bonding in these compounds and show that the newly formed E-E bonding interactions can be described as weak single σ-bond with no significant π-bonding contribution for E=Al, Ga. A large contribution to the dimer binding enthalpies results from London dispersion forces.

Original languageEnglish
Pages (from-to)447–455
Number of pages9
JournalChemistry - A European Journal
Issue number2
Publication statusPublished - 2017


  • Group13 elements
  • Low valent main group compounds
  • Metal-metal interactions
  • N-ligands
  • O-O activation

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