Group 13 metathesis: a route to group 13 multiple bonds Ella Rice, Dr Gary S. Nichol, Dr Michael J. Cowley University of Edinburgh, UK Newly-accessible low oxidation-state aluminium compounds have raised interest in the chemistry of compounds with multiple bonds to group 13 elements. In the past two years, the first phosphaalumene and phosphagallenes have been reported, 1,2 complementing recently-reported Al=NR systems. 3,4 They have shown impressive catalytically relevant bond activation processes. 5,6 Typically, these newly available E=PR and E=NR (E = Al, Ga) systems are accessed by direct combination of a low-oxidation state Al(I) or Ga(I) compounds and phosphinidene (PR) or nitrene (NR) fragments. Consequently, access to E=PR compounds is currently limited by the available E(I) precursors, of which only a handful exist and are difficult to synthesize. Here, I will present the direct preparation of phosphaalumenes and phosphagallenes from Al(III) and Ga(III) dihydrides. The reaction uses a phosphaborene (RP=BR) as a phosphinidene transfer reagent, and proceeds by a ‘group-13 metathesis’ process that is enabled by initial hydroalumination/hydrogallation of the P=B bond. I will also present the small molecule activation chemistry of phosphaallumene and phosphagallene compounds. References 1. Wilson, D. W.; Feld, J.; Goicoechea, J. M. Chem. Int. Ed . 2020 , 59 , 20914–20918. 2. Fischer, M.; Nees, S.; Kupfer, T.; Goettel, J. T.; Braunschweig, H. Am. Chem. Soc. 2021 , 143 , 4106–4111. 3. Heilmann, A.; Hicks, J.; Vasko, P.; Goicoechea, J.M.; Aldridge, S. Chem. 2020 , 132 , 4927–4931.
4. Anker, M. D.; Schwamm, R. J.; Coles, M. P.; Commun. 2020 , 56 , 2288–2291. 5. Feld, J.; Wilson, D. W. N.; Goicoechea. J. Chem. Int. Ed . 2021 , 60 , 22057–22061. 6. Sharma, M. K.; Wolper, C.; Haberhauer, G.; Schulz, S. Chem. Int. Ed . 2021 , 60 , 6784–6790.
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