To Bond or Not to Bond: Metal–Metal Interaction in Heterobimetallic Rare-Earth Metal–Silver Complexes

[Image: see text] The reaction of 2,4-(t)Bu(2)-6-(PPh(2))PhOH (HOAr(P)) with silver(I) triflate in a 3:1 molar ratio gave the mononuclear coinage metal complex (HOAr(P)-κP)(3)Ag(I)OTf (1). Treatment of HOAr(P) with Ln(III)[N(SiMe(3))(2)](3) (Ln = La, Sm, Y, Yb) in a 3:1 molar ratio yielded the mononuclear rare-earth metal complexes Ln(III)(OAr(P)-κ(2)O,P)(3) (2-Ln). The heterobimetallic rare-earth metal–silver complexes Ln(III)(OTf)(μ-OAr(P)-1κ(1)O,2κ(1)P)(3)Ag(I) (3-Ln) were prepared from monometallic precursors by reactions of equimolar amounts of 1 with Ln(III)[N(SiMe(3))(2)](3) or 2-Ln with silver(I) triflate, respectively. The compounds were characterized by NMR, ultraviolet–visible (UV–vis), and infrared (IR) spectroscopy, single-crystal X-ray diffraction, elemental analysis, and the effective magnetic moments of the paramagnetic complexes were determined via the Evans NMR method. Computational studies were conducted on 3-La and 3-Y.