Synthesis and crystal structures of tetrameric [2-(4,4-dimethyl-2-oxazolin-2-yl)anilido]sodium and tris[2-(4,4-dimethyl-2-oxazolin-2-yl)anilido]ytterbium(III)

Reaction of 2-(4,4-dimethyl-2-oxazolin-2-yl)aniline (H 2 - L1 ) with one equivalent of Na[N(SiMe 3 ) 2 ] in toluene afforded pale-yellow crystals of tetrameric poly[bis[μ 3 -2-(4,4-dimethyl-2-oxazolin-2-yl)anilinido][μ 2 -2-(4,4-dimethyl-2-oxazolin-2-yl)aniline]tetrasodium(I)], [Na 4 (C 11 H 13 N 2 O) 4 ] n or [Na 4 (H- L1 ) 4 ] n ( 2 ), in excellent yield. Subsequent reaction of [Na 4 (H- L1 ) 4 ] n ( 2 ) with 1.33 equivalents of anhydrous YbCl 3 in a 50:50 mixture of toluene–THF afforded yellow crystals of tris[2-(4,4-dimethyl-2-oxazolin-2-yl)anilinido]ytterbium(III), [Yb(C 11 H 13 N 2 O) 3 ] or Yb(H- L1 ) 3 ( 3 ) in moderate yield. Direct reaction of three equivalents of 2-(4′,4′-dimethyl-2′-oxazolinyl)aniline (H 2 - L1 ) with Yb[N(SiMe 3 ) 2 ] 3 in toluene resulted in elimination of hexamethyldisilazane, HN(SiMe 3 ) 2 , and produced Yb(H- L1 ) 3 ( 3 ) in excellent yield. The structure of 2 consists of tetrameric Na 4 (H- L1 ) 4 subunits in which each Na + cation is bound to two H- L1 bridging bidentate ligands and these subunits are connected into a polymeric chain by two of the four oxazoline O atoms bridging to Na + cations in the adjacent tetramer. This results in two 4-coordinate and two 5-coordinate Na + cations within each tetrameric unit. The structure of 3 consists of a distorted octahedron where the bite angle of ligand L1 ranges between 74.72 (11) and 77.79 (11) degrees. The oxazoline (and anilide) N atoms occupy meridional sites such that for one ligand an anilide nitrogen is trans to an oxazoline nitrogen while for the other two oxazoline N atoms are trans to each other. This results in a significantly longer Yb—N(oxazoline) distance [2.468 (3) Å] for the bond trans to the anilide compared to those for the oxazoline N atoms trans to one another [2.376 (3), 2.390 (3) Å].