[bis(2,5-di-tert-butylphospholyl)(tetrhydrofuran)thulim(II)] | 871584-29-1

• 英文名称: [bis(2,5-di-tert-butylphospholyl)(tetrhydrofuran)thulim(II)]
• 英文别名: [(2,5-di-tert-butylphospholyl)2Tm(THF)]；[(Htp)2Tm(THF)]
• CAS: 871584-29-1
• 化学式: C₂₈H₄₈OP₂Tm
• 分子量: 631.57
• InChiKey: KGXJBPZSJZSJQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  tris(tetrhydrofuran)diiodothulium(II) 、 sodium 2,5-di-tert-butylphospholyl 以 乙醚 为溶剂， 以38%的产率得到[bis(2,5-di-tert-butylphospholyl)(tetrhydrofuran)thulim(II)]
  参考文献：
  名称：

  二价铥与取代的磷酰基和环戊二烯基配体的新型配合物

  摘要：

  为了尝试使用在 3 和 4 位缺少甲基的磷酰配体来稳定 Tm-II 离子，制备了以下配体前体：2,5-二叔丁基磷酰钠 [Na(Htp)] (3)和 2,5-双（三甲基甲硅烷基）磷酸钠 [Na(Hsp)] (8)。由于其空间体积相似，我们还决定使用二叔丁基环戊二烯基 jNaCp(tt) (9) 作为配体前体。通过 2,5,2',5'-四叔丁基-1,1'-二磷酸 (2) 的 PP 键的钠裂解获得化合物 3。在 1,4-二碘-1,4-双(三甲基甲硅烷基)丁-1,3-二烯 (4) 中进行卤素-锂交换，然后与 PhPCl2 反应得到 1-苯基-2,5-双(三甲基甲硅烷基)磷 (5 ）。用锂金属处理 5 然后用碘氧化处理得到 2,5,2',5'-四（三甲基甲硅烷基）-1,1' -diphosphole (7) 可以通过钠处理转化为 8。在乙醚中用 [TmI2(THF)(3)] 处理 3、8 和 9 产生三种新的有机铥

  DOI：

  10.1002/ejic.200400784

文献信息

• Synthesis and Reactivity of Organometallic Complexes of Divalent Thulium with Cyclopentadienyl and Phospholyl Ligands
  作者：Florian Jaroschik、François Nief、Xavier-Frédéric Le Goff、Louis Ricard

  DOI：10.1021/om700316a

  日期：2007.7.1

  Reaction of sodium 1,2,4-tris(trimethylsilyl)cyclopentadienide [Na(Cp' '')] with [TmI2(THF)(3)] afforded the divalent thulium complex [(Cp' '')(2)Tm(THF)]. Its crystal structure is similar to that of the previously described [(Cp-ttt)(2)Tm(THF)] (Cp-ttt = 1,2,4-tris(tert-butyl)cyclopentadienyl). [(Cp' '')(2)TmI] was prepared by reaction of TmI3 with [K(Cp' '')] and could be reduced by KC8 into a new unsolvated, homoleptic complex, [(Cp' '')(2)Tm], which was characterized by NMR. [(Cp' '')(2)Tm] gave [(Cp' '')(2)Tm(THF)] by interaction with THF. A convenient alternative pathway to [(Cp-ttt)(2)Tm] by reduction of [(Cp-ttt)(2)Tm(BH4)] with KC8 was found: [(Cp-ttt)(2)Tm(BH4)] derives from [Tm(BH4)(3)(THF)(3)], which can be prepared from the less expensive TmCl3. On the other hand, the dimer [(Cp-tt)(2)TmI}(2)] (Cp-tt = 1,3-bis(tert-butyl)cyclopentadienyl), obtained by reaction of TmI3 with [Na(Cp-tt)], gave only intractable results by reaction with KC8. The previously described Tm-II complex [(Dtp)(2)Tm] (Dtp = 2,5-di-tert-butyl-3,4-dimethylphospholyl) and the new, homoleptic, structurally characterized Tm-II dimer [(Htp)(2)Tm}(2)] (Htp = 2,5-di-tert-butylphospholyl) were prepared by KC8 reduction of [(Dtp)(2)TmI] and [(Htp)(2)TmI}(2)], respectively. Reaction of [(Cp-ttt)(2)Tm] with pyridine resulted in an immediate reduction of pyridine into 1,1'-bis(1,4-dihydropyridylamide) and the formation of the structurally characterized [(Cp-ttt)(2)Tm}(2)mu-(NC5H5-C5H5N)}], while the reaction of [(Dtp)(2)Tm] with pyridine gave no isolable complexes. An NMR study suggests that initially a simple Tm-II adduct such as [(Dtp)(2)Tm(pyridine)] is formed in this reaction.