The diphosphino-alane ligand ClAl[C6H4(o-P-i-Pr-2)](2) (1) has been prepared and reacted with [AuCl(SMe2)]. X-ray analyses and DFT calculations substantiate the preference of the ensuing complex 2 for a zwitterionic structure, resulting from internal chloride abstraction by aluminum over a neutral form featuring an Au -> Al interaction.
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