Spirocyclic Boraamidinate Complexes of Lanthanide(III) Metals

The reaction of Li 2 [Ph bam Dipp ] (Ph bam Dipp = PhB(NDipp) 2 ; Dipp = 2,6‐ i Pr 2 C 6 H 3 ) with lanthanum(III) triiodides Ln I 3 (THF) 3.5 ( Ln = La, Sm) in THF produces complexes of the type [Li(THF) 4 ] 2 [(Ph bam Dipp ) 2 Ln I], which were characterized in solution by multinuclear NMR spectroscopy and in the solid state by single‐crystal X‐ray structural determinations. The ion‐separated complexes are comprised of a spirocyclic anion in which two Ph bam Dipp ligands and an iodide ion are linked to the five‐coordinate metal atom; charge balance is provided by two tetrasolvated lithium ions [Li(THF) 4 ] + .