New complexes containing some early transition metals with benzylbis(2-ethoxyethyl)phosphine (L) have been prepared. Reaction of this potentially hemilabile terdentate ligand with TiCl4 afforded [TiCl4L]1. The crystal structure shows the metal to have a distorted-octahedral geometry, where the ligand acts as a P,O-bonding chelate. Reaction of 1 with AgBF4 and AgO3SCF3 afforded yellow oils which could not be fully characterised, but are tentatively assigned as [TiCl3L][BF4] and [TiCl3L][O3SCF3] respectively. The reaction of [Cr(MeCN)3(CO)3] with L resulted in the formation of [Cr(CO)4L2]2 in poor yield. This complex can be prepared in high yield by the reaction of [Cr(MeCN)2(CO)4] with L. The reaction of [M(CO)3(C6H3Me3-2,4,6)](M = Mo or W) with L gave the complex fac-[Mo(CO)3L2]3 and [M(CO)4L2](M = Mo 4 or W 5) depending upon reaction conditions. The crystal structure of 3 shows the metal to have a distorted-octahedral geometry, where one L bonds as a P,O chelate and the other as a P-donor. 31P-1H} NMR spectroscopy indicates this complex to be fluxional in solution, where the two ligands readily interchange at high temperatures. The iron(II) complex [FeL2(O3SCF3)2]6 was prepared by the reaction of L and FeCl2·4H2O with AgO3SCF3. Its crystal structure shows the metal to have a distorted-octahedral geometry with trans ligands (through phosphorus and oxygen) and trans-co-ordinating triflates.
已制备出含有一些早期过渡
金属与苄基双(
2-乙氧基乙基)膦(L)的新络合物。这种潜在的半不稳定三齿
配体与 TiCl4 反应得到 [TiCl4L]1。晶体结构显示该
金属具有扭曲的八面体几何形状,其中
配体充当 P,O 键合螯合物。 1 与
AgBF4 和 AgO3SCF3 反应得到黄色油状物,无法完全表征,但暂时分别指定为 [TiCl3L][BF4] 和 [TiCl3L][O3SCF3]。 [Cr(MeCN)3(CO)3] 与 L 的反应导致形成 [Cr(CO)4
L2]2,但产率较低。该配合物可以通过 [Cr(MeCN)2(CO)4] 与 L 的反应以高产率制备。 [M(CO)3(C6H3Me3-2,4,6)](M = Mo 或W) 与 L 得到配合物 fac-[Mo(CO)3
L2]3 和 [M(CO)4
L2](M = Mo 4 或 W 5),具体取决于反应条件。 3 的晶体结构显示该
金属具有扭曲的八面体几何形状,其中一个 L 作为 P,O 螯合物键合,另一个作为 P-供体。 31P-1H} NMR 光谱表明该配合物在溶液中是流动的,其中两个
配体在高温下很容易互换。 L和FeC
L2·4H2O与AgO3SCF3反应制备了
铁(II)配合物[Fe
L2(O3SCF3)2]6。其晶体结构显示该
金属具有带有反式
配体(通过
磷和氧)和反式配位
三氟甲磺酸酯的扭曲八面体几何形状。