A Neutral Dy(II) Bis(amide): Synthesis, Magnetism, and a P₄^2– Complex

High Resolution Image Download MS PowerPoint Slide Reaction of DyCl 3 with KNHAr*, where Ar* = 2,6-Ar 2 C 6 H 3 and Ar = 2,4,6- i Pr 3 C 6 H 2, results in the formation of ClDy(NHAr*) 2, which can be reduced with KC 8 in THF to room temperature stable dysprosium(II) Dy(NHAr*) 2, where Ar rings of the NHAr* ligand chelate and bind to the metal center to give a black sandwich complex. The redox potential for the reversible Dy 2+/3+ -couple was found to be −1.094 ± 0.001 V with respect to FeCp 2 +/0 as 0.000 V. The complex was examined by CASSCF calculations, which suggest the non-Kramer’s ion has an 4f 9 5d 1 -configuration with little to no s -orbital participation. The reaction of Dy(NHAr*) 2 with CN t Bu results in assumed tert -butyl radical loss along with formation of the isocyanide CN–Dy(NHAr*) 2, which shows a strong absorption in the IR spectrum at 2052 cm –1 assigned to the C–N stretch. Reaction of P 4 with Dy(NHAr*) 2 gave crystals of salt {Dy(NHAr*) 2 } + {(P 4 )Dy(NHAr*) 2 } −, which shows both η 2 -P 4 2– and η 4 -P 4 2– ligands in the solid state.