摘要 : A new synthetic route based on bis(3,5-dimethylpyrazol-1-yl)acetic acid (Hbdmpza) (1) has afforded the alcohol 2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol (Hbdmpze) in good yield. This alcohol and the related lithium compound [{Li(bd... 展开 A new synthetic route based on bis(3,5-dimethylpyrazol-1-yl)acetic acid (Hbdmpza) (1) has afforded the alcohol 2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol (Hbdmpze) in good yield. This alcohol and the related lithium compound [{Li(bdmpza)(H_2O)}_4] are excellent precursors for introducing these scorpionate ligands into transition metal complexes. For example, the lithium compound and Hbdmpze (the latter after prior addition of nBuLi) react with a solution of MCl_5 (M = Nb, Ta) in THF to give, after stirring for 12 h at -70 ℃, a solution from which the complexes [MCl_4(κ~3-bdmpzx)] (x = a, M = Nb 2, Ta 3; x = e, M = Nb 4, Ta 5) have been isolated. When solutions of 2-5 in THF were stirred at ca. 20 ℃ for 48 h, the oxo complexes [MCl_2(O)(κ~3-bdmpzx)] (x = a, M = Nb 6, Ta 7; x = e, M = Nb 8, Ta 9) were isolated. The structures of these complexes have been determined by spectroscopic methods and the X-ray crystal structure of 8 has been established. Finally, a new class of heteroscorpionate-metal complexes containing an alkoxide ligand has been prepared. Direct reaction of the complexes [MCl_4(κ~3-bdmpza)] (M = Nb 2, Ta 3) with several alcohols gave the complexes [MCl3(3-bdmpza)(OR)] (M = Nb, R = Me 10, Et 11, iPr 12, tBu 13; M = Ta, R = Me 14, Et 15, iPr 16, tBu 17) after the appropriate workup. 收起