Ishida Yutaka, Kawaguchi Hiroyuki
Department of Chemistry, Tokyo Institute of Technology , Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
Inorg Chem. 2014 Jul 7;53(13):6775-87. doi: 10.1021/ic5005853. Epub 2014 Jun 16.
The anilide-bis(aryloxide) proligands H3[ONO(R)] (where H3[ONO(R)] = 2,6-(3-R(1)-5-R(2)-2-hydroxybenzyl)-4-tert-butyl-N-tolyl-aniline; H3[ONO(tBu)], R(1) = (t)Bu, R(2) = Me; H3[ONO(Me)], R(1) = Me, R(2) = (t)Bu; H3[ONO(Me2)], R(1) = R(2) = Me) were synthesized from 2-bromo-5-tert-butyl-isophthalic acid dimethyl ester in three steps in multigram scale. The ligand precursor H3[ONO(tBu)] was readily doubly and triply deprotonated with alkali metal reagents to generate the related derivatives M2[H(ONO(tBu))] and M3[ONO(tBu)] (M = Li, Na, K). The extent of ligand deprotonation is observed to depend on the choice of deprotonating reagents and solvents. Transmetalation reaction of the trilithium derivative Li3[ONO(tBu)] with MCl3(THF)3 (M = Cr, V; THF = tetrahydrofuran) afforded [(ONO(tBu))CrCl(THF){Li(THF)}] (5) and [(ONO(tBu))V(THF)] (6). The vanadium complex 6 reacted readily with 2-butyne, styrene oxide, and mesityl azide, yielding [(ONO(tBu))V(η(2)-MeCCMe)] (7), [(ONO(tBu))V(O)] (8), and [(ONO(tBu))V(NMes)] (9), respectively. The solid-state structures of H3[ONO(tBu)] and metal complexes were determined by X-ray crystallography. The [ONO(tBu)] ligand adopts a u-shaped structure in solution and solid state.
酰胺基双（芳氧基）前体配体H3[ONO(R)]（其中H3[ONO(R)] = 2,6-(3-R(1)-5-R(2)-2-羟基苄基)-4-叔丁基-N-甲苯基苯胺；H3[ONO(tBu)]，R(1) = (t)Bu，R(2) = Me；H3[ONO(Me)]，R(1) = Me，R(2) = (t)Bu；H3[ONO(Me2)]，R(1) = R(2) = Me）由2-溴-5-叔丁基-间苯二甲酸二甲酯分三步以多克规模合成。配体前体H3[ONO(tBu)]很容易被碱金属试剂双重和三重去质子化，生成相关衍生物M2[H(ONO(tBu))]和M3[ONO(tBu)]（M = Li、Na、K）。观察到配体去质子化的程度取决于去质子化试剂和溶剂的选择。三锂衍生物Li3[ONO(tBu)]与MCl3(THF)3（M = Cr、V；THF = 四氢呋喃）的金属转移反应得到[(ONO(tBu))CrCl(THF){Li(THF)}]（5）和[(ONO(tBu))V(THF)]（6）。钒配合物6很容易与2-丁炔、环氧苯乙烷和均三甲苯基叠氮反应，分别生成[(ONO(tBu))V(η(2)-MeCCMe)]（7）、[(ONO(tBu))V(O)]（8）和[(ONO(tBu))V(NMes)]（9）。通过X射线晶体学确定了H3[ONO(tBu)]和金属配合物的固态结构。[ONO(tBu)]配体在溶液和固态中采用u形结构。
