Out of the 14 lanthanide (Ln) ions, molecular complexes of Ln(IV) were known only for cerium and more recently terbium. Here we demonstrate that the +IV oxidation state is also accessible for the large praseodymium (Pr) cation. The oxidation of the tetrakis(triphenysiloxide) Pr(III) ate complex, [KPr(OSiPh 3 ) 4 (THF) 3 ], 1-Pr Ph , with [N(C 6 H 4 Br) 3 ][SbCl 6 ], affords the Pr(IV) complex [Pr(OSiPh 3 ) 4 (MeCN) 2 ], 2-Pr Ph , which is stable once isolated. The solid state structure, UV−visible spectroscopy, magnetometry, and cyclic voltammetry data along with the DFT computations of the 2-Pr Ph complex unambiguously confirm the presence of Pr(IV).
Nd, like U, prefers a f4 configuration with the tris(aryloxide)arene ligand rather than the 4f35d1 configuration found in tris(cyclopentadienyl) complexes.
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