Synthesis and Structural Characterization of Lithium and Titanium Complexes Bearing a Bulky Aryloxide Ligand Based on a Rigid Fused-Ring s-Hydrindacene Skeleton.
The bulky aryl alcohols, (Rind)OH (1) [Rind = EMind (a) and Eind (b)], based on the rigid fused-ring 1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacene skeleton were prepared by the reaction of (Rind)Li with nitrobenzene followed by protonation. The treatment of 1 with (n)BuLi affords the lithium aryloxide dimers [(Rind)OLi(THF)]2 (2) or trimers [(Rind)OLi]3 (3), depending on the employed solvents (THF = tetrahydrofuran). The salt metathesis reaction of [(EMind)OLi(THF)]2 (2a) with TiCl4(THF)2 leads to the formation of the mononuclear diamagnetic mono- and bis(aryloxide) Ti(IV) complexes, [(EMind)O]TiCl3(THF) (4a) and [(EMind)O]2TiCl2 (5a). We also isolated a trace amount of the tris(aryloxide) Ti(IV) complex, [(EMind)O]3TiCl (6a). The reaction between 2a and TiCl3(THF)3 resulted in the isolation of the mononuclear paramagnetic mono- and bis(aryloxide) Ti(III) complexes, [(EMind)O]TiCl2(THF)2 (7a) and [(EMind)O]2TiCl(THF)2 (8a). The discrete monomeric structures of the titanium complexes 4a, 5a, 6a, 7a, and 8a were determined by X-ray crystallography.
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University , 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.
Shoya
S
Kanazawa
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University , 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.
Taishi
T
Ohira
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University , 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.
Shun
S
Goda
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University , 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.
Naoki
N
Hayakawa
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University , 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.
Tomoharu
T
Tanikawa
Materials Characterization Support Unit, RIKEN Center for Emergent Matter Science , 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Daisuke
D
Hashizume
Department of Chemistry, Tokyo Institute of Technology , 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
Yutaka
Y
Ishida
Department of Chemistry, Tokyo Institute of Technology , 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan.|Japan Science and Technology Agency, ACT-C , 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan.
Hiroyuki
H
Kawaguchi
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University , 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.|Japan Science and Technology Agency, ACT-C , 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan.
Tsukasa
T
Matsuo