NEUTRAL AND CATIONIC GROUP 4 METAL COMPOUNDS CONTAINING OCTAMETHYLDIBENZOTETRAAZAANNULENE (ME8TAA2-) LIGANDS. SYNTHESIS AND REACTIVITY OF (ME8TAA)MX2 AND (ME8TAA)MX+ COMPLEXES (M = ZR, HF; X = CL, HYDROCARBYL, NR2, OR)

The synthesis and reactivity of out-of-plane (Me8taa)MX2 and (Me8taa)MX+ complexes (M= Zr, Hf; X= Cl, hydrocarbyl, NR2, OR) containing the dianionic tetraaza-macrocycle ligand octamethyldibenzotetraazaannulene (Me8taa2-) are described. The reaction of [Li(Et2O)]2[Me8taa] (1) with MCl4(THF)2 yields (Me8taa)MCl2 complexes (2a, M = Zr; 2b, M = Hf). Alkylation of 2a,b with LiCH2SiMe3 or LiMe in hydrocarbon solvents yields (Me8taa)M(CH2SiMe3)2 (3a, M = Zr; 4a, M = Hf) or (Me8taa)MMe2 (3b, M = Zr; 4b, M = Hf) complexes. Compound 3b rearranges by migration of a Me group from Zr to a Me8taa imine carbon in coordinating solvents. The reaction of (Me8taa)H2 with the appropriate ZrR4 compound yields (Me8taa)Zr(CH2Ph)2 (3c) and (Me8taa)Zr(CH2CMe3)2 (3d). The reaction of (Me8taa)H2 and Zr(NR2)4 yields (Me8taa)Zr(NR2)2 (6a, R = Me; 6b, R = Et). Spectroscopic data for (Me8taa)MX2 compounds 2, 3, 4, and 6 are consistent with cis, C2v-symmetric structures. Dialkyl complexes 3 and 4 and bis(amide) complexes 6 react with ch...