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Heterobimetallic Pd(0) complexes with Pd→Ln (Ln = Sc, Y, Yb, Lu) dative bonds: rare-earth metal-dominated frustrated Lewis pair-like reactivity.

A series of heterobimetallic Pd-Ln complexes with Pd→Ln (Ln = Sc, Y, Yb, Lu) dative bonds were synthesized via sequential reactions of phosphinoamine Ph2PNHAd with (Me3SiCH2)3Ln(THF)2 and (Ph3P)4Pd or (COD)Pd(CH2SiMe3)2. These complexes were characterized by NMR spectroscopy, X-ray diffractions, and computational as well as electrochemical studies, which revealed Pd→Ln dative interactions that vary according to the ionic radii of Ln3+. Furthermore, the notable dynamic structural features of the Pd-Ln complexes in solution and their unexpected frustrated Lewis pair-like reactivity toward aryl halides and ketene were also studied.