Tm(tris-tert-butylcyclopentadienyl)2 | 878168-20-8

• 英文名称: Tm(tris-tert-butylcyclopentadienyl)2
• 英文别名: bis(1,2,4-tris(tert-butyl)cyclopentadienyl)thulium(II)；Tm(tris-tert-butylcyclopentadienyl)₂；Tm(Cpttt)₂；[(Cp(ttt))2Tm]；(Cpttt)2Tm
• CAS: 878168-20-8
• 化学式: C₃₄H₅₈Tm
• 分子量: 635.769
• InChiKey: CAFDBLUAXGBGDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  silver(I) iodide 、 Tm(tris-tert-butylcyclopentadienyl)2 以 四氢呋喃 为溶剂， 以38%的产率得到bis(1,2,4-tris(tert-butyl)cyclopentadienyl)thulium(III) iodide
  参考文献：
  名称：

  通过还原a（III）前体合成新型稳定的中性有机organo（II）配合物。

  摘要：

  新的稳定的中性Tm（II）络合物（Cp（ttt））2Tm [Cp（ttt）= 1,2,4-三（叔丁基）环戊二烯基]可以通过NaCp（ttt）与TmI2或通过在非极性溶剂中还原（Cp（ttt））2TmI来实现；后一种路线可能证明对分离其他中性非经典低价有机镧系元素很有用。

  DOI：

  10.1039/b514818a
• 作为产物：
  描述：

  bis(1,2,4-tris(tert-butyl)cyclopentadienyl)thulium(III) iodide 在 KC₈ 作用下， 以 甲苯 为溶剂， 以47%的产率得到Tm(tris-tert-butylcyclopentadienyl)2
  参考文献：
  名称：

  通过还原a（III）前体合成新型稳定的中性有机organo（II）配合物。

  摘要：

  新的稳定的中性Tm（II）络合物（Cp（ttt））2Tm [Cp（ttt）= 1,2,4-三（叔丁基）环戊二烯基]可以通过NaCp（ttt）与TmI2或通过在非极性溶剂中还原（Cp（ttt））2TmI来实现；后一种路线可能证明对分离其他中性非经典低价有机镧系元素很有用。

  DOI：

  10.1039/b514818a

文献信息

• FIRST EXAMPLES OF MOLECULAR POLYCHALCOGENIDE COMPLEXES OF THULIUM
  作者：A. G. Demkin、B. Yu. Savkov、T. S. Sukhikh、S. N. Konchenko

  DOI：10.1134/s0022476621060159

  日期：2021.6

  16-hexaoxa cyclooctadecane) (3). A reaction of complex 2 with CS2 in toluene is studied. It results in \([(\textCp}'''_2 \textTm})_2(\mu-\eta^2:\eta^1\text-CS}_4)]\) compound (4) that is the first example of Tm(III) perthiocarbonate complex. Structures of 2-4 are determined by single crystal X-ray diffraction.

  摘要 通过\([\textCp}'''_2 \textTm}]\) (Cp''' = 1,3,4-tris( tert - butyl)环戊二烯化物) ( 1 ) 与元素硫在不同条件下：\([(\textCp}'''_2 \textTm})_2(\mu-\eta^2:\eta^2\text-S }_2)]\) ( 2 ) 和\([\textK}(18\text-cr-}6)][\textCp}'''_2 \textTm}(\eta^2 \text-S}_2)]\) (18-cr-6 – 1,4,7,10,13,16-hexaoxa cyclooctadecane) ( 3 )。研究了络合物2与 CS 2在甲苯中的反应。结果是\([(\textCp}'''_2 \textTm})_2(\mu-\eta^2:) 这是 Tm(III) 过硫代碳酸酯复合物的第一个例子。的结构2
• 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.
• Synthesis and Characterization of 1,1′-Diphosphaplumbocenes: Oxidative Ligand Transfer Reactions with Divalent Thulium Complexes
  作者：Florian Jaroschik、Aurélien Momin、Agathe Martinez、Dominique Harakat、Louis Ricard、Xavier Frédéric Le Goff、Grégory Nocton

  DOI：10.1021/acs.organomet.6b00313

  日期：2016.6.13

  The new 1,1'-diphosphaplumbocenes Pb(Dtp)(2) (Dtp = 2,5-di-tert-butyl-3,4-dimethylphospholyl) and Pb(Dsp)(2) (Dsp = 2,5-ditrimethylsilyl-3,4-dimethylphospholyl) have been synthesized and characterized by multinuclear NMR spectroscopy. Pb-207 NMR spectra of both complexes, as well as for the known complex Pb(Htp)(2) (Htp = 2,5-di-tert-butylphospholyl), show that the phospholyl ligands lead to an important downfield shift compared with that of cyclopentadienyl based plumbocenes. X-ray diffraction studies of the Pb(Dtp)(2) complex revealed a structure with two slightly bent eta(5)-bound ligands. This complex was employed in the oxidative ligand transfer reaction with bulky divalent thulium complexes. In the case of Tm(Dtp)(2), the first example of a monomeric trivalent tris(phospholyl)lanthanide complex Tm(Dtp)(3) was obtained. X-ray diffraction studies and low-temperature H-1 NMR studies show the eta(1) coordination mode of the third Dtp ligand. In contrast, oxidation of Tm(Cp-ttt)(2) (Cp-ttt is for tris-tert-butylcyclopentadienyl) led presumably to the formation of the ion pair complex [Tm(Cp-ttt)(2)] [Dtp], in which no interaction between the free Dtp ligand and Tm was observed, as shown by variable temperature H-1 and P-31 NMR studies. The new trivalent complexes could be reduced back to the original divalent complexes with potassium graphite.