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

Abstract

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.