Synthesis, structures and reactions of lithium complexes of [(o-RCHC6H4)PPh2=NSiMe3]-(R = H, SiMe3) ligands.
Synthesis, structures and reactions of lithium complexes of [(o-RCHC6H4)PPh2=NSiMe3]-(R = H, SiMe3) ligands.
复制标题
[(o-RCHC6H4)PPh2=NSiMe3]-(R = H, SiMe3)配体锂配合物的合成、结构和反应。
作者：
Zhong‐Xia Wang;Chun
N-三甲基甲硅烷基邻甲基苯基二苯基膦亚胺，(o-MeC6H4)PPh2=NSiMe3 (1)，是通过 Ph2P(Br)=NSiMe3 与邻甲基苯基锂反应制备的。用 LiBun 处理 1，然后用 Me3SiCl 处理，得到 (o-Me3SiCH2C6H4)PPh2=NSiMe3 (2)。在 tmen 存在下，1 和 2 与 LiBu(n) 的锂化得到结晶锂配合物 [Li{CH(R)C6H4(PPh(2=NSiMe3)-.tmen](3, R = H; 4, R = SiMe3)。从 4 的母液中，可以看到 tmen 桥接配合物的痕迹得到[Li{CH(SiMe3)C6H4(PPh2=NSiMe3)-2}]2(mu-tmen) (5) 2 与LiBun 在Et2O 中反应得到络合物[Li{CH(SiMe3)C6H4(PPh2=NSiMe3)-2}.OEt2] (6) 与Me2SiCl2 以2:1 摩尔比反应得到。二甲基甲硅烷基桥接化合物 Me2Si[CH2C6H4(PPh2=NSiMe3)-2]2 (7) 用两当量的 LiBun 在 Et2O 中锂化，得到 [Li2{(CHC6H4(PPh2=NSiMe3)-2)2SiMe2}.0.5OEt2](8.0.5OEt2) 用 PhCN 处理形成烯酰胺锂络合物。 [Li{N(SiMe3)C(Ph)CHC6H4(PPh2=NSiMe3)-2}.tmen] (9) 两当量的 5 与 1,4-二氰基苯反应得到二锂络合物 [{Li(OEt2)2}2(1,4-{C(N(SiMe3)CHC6H4(PPh2=NSiMe3)-2}2C6H4)]。 (10).所有化合物均通过NMR光谱和元素分析进行了表征。化合物2、3、5、6和9的结构均已通过单晶X射线衍射技术确定。
N-Trimethylsilyl o-methylphenyldiphenylphosphinimine, (o-MeC6H4)PPh2=NSiMe3 (1), was prepared by reaction of Ph2P(Br)=NSiMe3 with o-methylphenyllithium. Treatment of 1 with LiBun and then Me3SiCl afforded (o-Me3SiCH2C6H4)PPh2=NSiMe3 (2). Lithiations of both 1 and 2 with LiBu(n) in the presence of tmen gave crystalline lithium complexes [Li{CH(R)C6H4(PPh(2=NSiMe3)-.tmen](3, R = H; 4, R = SiMe3). From the mother liquor of 4, traces of the tmen-bridged complex [Li{CH(SiMe3)C6H4(PPh2=NSiMe3)-2}]2(mu-tmen) (5) were obtained. Reaction of 2 with LiBun in Et2O yielded complex [Li{CH(SiMe3)C6H4(PPh2=NSiMe3)-2}.OEt2] (6). Reaction of lithiated with Me2SiCl2 in a 2:1 molar ratio afforded dimethylsilyl-bridged compound Me2Si[CH2C6H4(PPh2=NSiMe3)-2]2 (7). Lithiation of 7 with two equivalents of LiBun in Et2O yielded [Li2{(CHC6H4(PPh2=NSiMe3)-2)2SiMe2}.0.5OEt2](8.0.5OEt2). Treatment of 4 with PhCN formed a lithium enamide complex [Li{N(SiMe3)C(Ph)CHC6H4(PPh2=NSiMe3)-2}.tmen] (9). Reaction of two equivalents of 5 with 1,4-dicyanobenzene gave a dilithium complex [{Li(OEt2)2}2(1,4-{C(N(SiMe3)CHC6H4(PPh2=NSiMe3)-2}2C6H4)] (10). All compounds were characterised by NMR spectroscopy and elemental analyses. The structures of compounds 2, 3, 5, 6 and 9 have been determined by single crystal X-ray diffraction techniques.