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Disturbing neighbors: Alkenylgold species with a heteroatom substituent are thought to be key intermediates in gold‐catalyzed trans additions of protic nucleophiles to alkynes. One reason for the scarcity of such compounds lies in the non‐innocence of the neighboring heteroatom, which may enforce the uptake of a second gold fragment with formation of surprisingly robust species with a gem‐digold unit...
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