Despite debate on intramolecular N→P interactions in peri-substituted naphthalene derivatives their coordination chemistry has not yet been reported. Herein, we describe bonding in and reactivity of dichloro(8-dimethylamino-1-naphthyl)phosphane towards pentacarbonyltungsten(0) reagents. A 1-aza-2-phospha-acenaphthene complex was obtained via the unexpected elimination of chloromethane enabled through P-coordination. Theoretical DFT calculations provide insights into P⋯N pnictogen bonding interaction as well as the reaction pathway of the elimination reaction.
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