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

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 -κ P ) 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 .