SYNTHESIS, PROPERTIES, STRUCTURAL CHARACTERIZATION, AND REACTIVITY OF LOW-VALENT TITANIUM (BISDIIMINE) COMPLEXES

The synthesis, structure, and reactivity of titanium bis(diimine) complexes supported by 1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion and 2,2\u27 methylene-bridged 4-methyl, 6-tertbutyl phenol ligands is reported. The molecular structure of [(DMSC)Ti(bpy)2] (28) and [(MBMP)Ti(bpy)2] (55) was characterized by X-ray crystallography. Complexes [(DMSC)Ti(bpy)2] (28), [(DMSC)Ti(dmbpy)2] (29), and [(DMSC)Ti(phen)2] (30) undergoes light-assisted reactions with two or more equivalents of (C6H5)2CO or (p-MeC6H4)2CO to give the corresponding 1-aza-5-oxa-titanacyclopentene complexes 37-42. Similar reactivity was observed with [(MBMP)Ti(bpy)2] (55), [(MBMP)Ti(dmbpy)2] (56), and [(MBMP)Ti(phen)2] (57). The molecular structure of [(MBMP)Ti{kappa-3-OC(C6H5)2C10H7N2}{OCH(C6H5)2}] (58) was characterized by 1H and 13C NMR as well as X-Ray crystallography