Liddle Stephen T, Arnold Polly L
School of Chemistry, University Park, University of Nottingham, Nottingham, UK.
Dalton Trans. 2007 Aug 14(30):3305-13. doi: 10.1039/b706971e. Epub 2007 Jun 20.
Reaction of YI(3)(THF)(3.5) with one equivalent of the potassium beta-diketiminate (BDI) complex [HC{C(CH(3))NAr}(2)K] (Ar = 2,6-Pr(i)(2)C(6)H(3)) affords the monomeric, mono-substituted yttrium BDI complex [HC{C(CH(3))NAr}(2)YI(2)(THF)] in good yield. Reaction of with DME affords [HC{C(CH(3))NAr}(2)YI(2)(DME)] in quantitative yield, which is monomeric also. Reaction of the primary terphenyl phosphane ArPH(2) (Ar = 2,6-(2,4,6-Pr(i)(3)C(6)H(2))(2)C(6)H(3)) with potassium hydride, and recrystallisation from hexane, affords the potassium primary terphenyl phosphanide complex [{ArP(H)K(THF)}(2)] in high yield. Compound is dimeric in the solid state, constructed around a centrosymmetric K(2)P(2) four-membered ring, the coordination sphere of potassium is supplemented with an eta(6) K[dot dot dot]C(aryl) interaction. The reaction of with one molar equivalent of in THF affords the THF ring-opened compound [HC{C(CH(3))NAr}(2)Y{O(CH(2))(4)P(H)Ar}(I)(THF)]. Compound is formed as a mixture of endo(OR) and exo(OR) isomers (: = approximately 2 : 1) which may be separated by fractional crystallisation from hexane-toluene to give pure . Attempted alkylation of with two equivalents of KCH(2)Si(CH(3))(3) affords the potassium yttriate complex [Y{micro-eta(5):eta(1)-ArNC(CH(3))[double bond, length as m-dash]CHC([double bond, length as m-dash]CH(2))NAr}(2)K(DME)(2)] in moderate yield; contains two dianionic dianilide ligands, which are derived from C-H activation of a backbone methyl group, each bonded eta(5) to yttrium in the solid state. The reaction of with one equivalent of KC(8) affords [{HC(C[CH(3)]NAr)(2)YI(micro-OCH(3))}(2)], derived from C-O bond activation of DME, as the only isolable product in very low yield. Compounds , , , , , and have been characterised by single crystal X-ray diffraction, NMR spectroscopy and CHN microanalyses.
YI(3)(THF)(3.5) 与一当量的 β-二酮亚胺钾 (BDI) 配合物 [HC{C(CH(3))NAr}(2)K](Ar = 2,6-Pr(i)(2)C(6)H(3))反应,以良好的产率得到单体单取代钇 BDI 配合物 [HC{C(CH(3))NAr}(2)YI(2)(THF)]。与 DME 反应以定量产率得到 [HC{C(CH(3))NAr}(2)YI(2)(DME)],它也是单体。一级三联苯膦 ArPH(2)(Ar = 2,6-(2,4,6-Pr(i)(3)C(6)H(2))(2)C(6)H(3))与氢化钾反应,并从己烷中重结晶,以高产率得到一级三联苯膦钾配合物 [{ArP(H)K(THF)}(2)]。该化合物在固态下是二聚体,围绕一个中心对称的 K(2)P(2) 四元环构建,钾的配位球通过 η(6) K[···]C(芳基) 相互作用得到补充。在 THF 中与一摩尔当量的 反应得到 THF 开环化合物 [HC{C(CH(3))NAr}(2)Y{O(CH(2))(4)P(H)Ar}(I)(THF)]。该化合物以 endo(OR) 和 exo(OR) 异构体的混合物形式形成(: = 约 2 : 1),可通过从己烷 - 甲苯中分步结晶分离得到纯品 。尝试用两当量的 KCH(2)Si(CH(3))(3) 对 进行烷基化反应,以中等产率得到钇酸钾配合物 [Y{μ-η(5):η(1)-ArNC(CH(3))[双键,长度如 m 破折号]CHC([双键,长度如 m 破折号]CH(2))NAr}(2)K(DME)(2)];含有两个双阴离子二苯胺配体,它们源自主链甲基的 C-H 活化,在固态下每个都以 η(5) 键合到钇上。与一当量的 KC(8) 反应得到 [{HC(C[CH(3)]NAr)(2)YI(μ-OCH(3))}(2)],它源自 DME 的 C-O 键活化,是唯一可分离的产物,产率极低。化合物 、 、 、 、 、 和 已通过单晶 X 射线衍射、NMR 光谱和 CHN 微量分析进行了表征。