1,1-bis(tetramethylphospholyl)dichlorozirconium | 112549-05-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 1,1-bis(tetramethylphospholyl)dichlorozirconium
• 英文别名: bis(η(5)-tetramethylphospholyl)dichlorozirconium；bis(η5-2,3,4,5-tetramethylphospholyl)dichlorozirconium；2,3,4,5-Tetramethyl-1-phosphanidacyclopenta-2,4-diene;zirconium(4+);dichloride；2,3,4,5-tetramethyl-1-phosphanidacyclopenta-2,4-diene;zirconium(4+);dichloride
• CAS: 112549-05-0
• 化学式: C₁₆H₂₄Cl₂P₂Zr
• 分子量: 440.444
• InChiKey: QWGUJKWQCXUZKX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  0.44
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-丁炔 、 1,1-bis(tetramethylphospholyl)dichlorozirconium 在 Mg 作用下， 以 四氢呋喃 为溶剂， 以80%的产率得到1,1-bis(tetramethylphospholyl)-2,3,4,5-tetramethylzirconacyclopenta-2,4-diene
  参考文献：
  名称：

  Generation and Trapping of a 1,1‘-Diphosphazirconocene

  摘要：

  The reduction of [(eta(5)-C4Me4P)(2)ZrCl2] (1) by magnesium in THF affords a transient octamethyl-1,1'-diphosphazirconocene which can be trapped by CO, bis(trimethylsilyl)acetylene, and 2-butyne to give the corresponding dicarbonyl 2, zirconacyclopropene 3, and zirconacyclopentadiene 4; all of these products have been characterized by X-ray analyses. An assessment of the,pi-basicity of the eta(5)-C4Me4P ligand has been made by several methods: (a) a comparison of the IR carbonyl stretching frequencies of 2 and of other dicarbonylzirconocene complexes, (b) a correlation of the C-13 NMR and IR data in 3 and in similar zirconacyclopropenes, and (c) an electrochemical study on 1. All these experiments confirm that the eta(5)-C4Me4P ligand is a poorer pi-base than the Cp ligand.

  DOI：

  10.1021/om010634u
• 作为产物：
  描述：

  (2,3,4,5-tetramethylphospholyl)bis(dimethylamido)zirconium chloride 在 trimethyl phosphorous borane 作用下， 以 氘代苯 为溶剂， 反应 14.0h， 生成 1,1-bis(tetramethylphospholyl)dichlorozirconium
  参考文献：
  名称：

  单硼烷苯和-磷酰基锆茂（IV）衍生物：迈向混合杂环锆茂复合物

  摘要：

  摘要为了扩展对锆的磷酰和硼酸苯络合物的化学反应的认识，已显示出潜在的聚合催化剂的作用，本研究旨在探索单硼酸苯和单磷酰锆络合物的合成，并研究它们对锆的反应性。混合形成（硼酸苯）（磷酰基）锆配合物。合成了（η5-磷酰基）Zr（NMe2）xCl3-x和（η6-硼根苯-NMe2）Zr（NMe2）xCl3-x的几种衍生物，并用作形成混合的（硼烷基苯）（磷酰基）锆络合物的前体。

  DOI：

  10.1016/j.poly.2015.07.037

文献信息

• Synthesis of Phospholyl-Bridged Heterobimetallic Ruthenium Hydrides in Combination with Zirconium and Ytterbium and the Crystal Structure of (THF)₂Yb[μ(η⁵,η¹)-C₄Me₄P]₂Ru(H)₂(Ph₃P)₂
  作者：P. Desmurs、M. Visseaux、D. Baudry、A. Dormond、F. Nief、L. Ricard

  DOI：10.1021/om9602320

  日期：1996.10.1

  Heterobimetallic zirconium-ruthenium and ytterbium-ruthenium dihydrides, having bridging phospholyl ligands, have been obtained for the first time. Reaction of bin(eta(5)-tetramethylphospholyl)dichlorozirconium [(TMP)(2)ZrCl2] with RuH4(PPh(3))(3) gave the zirconium-ruthenium heterobimetallic Cl2Zr[mu(eta(5),eta(1))-TMP]Ru-2(H)(2)(PPh(3))(2). This compound was transformed into the hydridochloride Cl2Zr[mu(eta(5),eta(1))-TMP]Ru-2(H)(Cl)(PPh(3))(2) by the action of CCl4. Similarly, reaction of [(TMP)(2)Yb] with RuH4(PPh(3))(3) afforded (THF)(2)Yb[mu(eta(5),eta(1))-TMP]Ru-2(H)(2)(PPh(3))(2). The structure of this compound, which has been determined by X-ray crystallography, confirms the trans configuration of the dihydride deduced previously from NMR data. Attempts to isolate products from the reaction of [(TMP)(2)UCl2] or [(TMP)(2)U(BH4)(2)] with RuH4(PPh(3))(3) were unsuccessful, but NMR data show the formation of both heterobimetallic trans- and cis-ruthenium dihydride-uranium compounds X(2)U[mu(eta(5),eta(1))-TMP]Ru-2(H)(2)(PPh(3))(2) (X = BH4, Cl) in solution.
• Reactivity of a diphosphazirconocene dichloride, (η5-C4Me4P)2ZrCl2. Crystal and molecular structure of a metal-bridged bis(π-heterocyclopentadienyl)zirconium complex, (CO)3Fe(μ-η5,η1-C4Me4P)2ZrCl2
  作者：François Nief、François Mathey、Louis Ricard

  DOI：10.1016/0022-328x(90)87120-3

  日期：1990.3
• Nief, François; Mathey, François; Ricard, Louis, Organometallics, 1988, vol. 7, # 4, p. 921 - 926
  作者：Nief, François、Mathey, François、Ricard, Louis、Robert, Francis

  DOI：——

  日期：——
• Mono-boratabenzene and -phospholyl zirconocene(IV) derivatives: Towards mixed heterocycles zirconocene complexes
  作者：Guillaume Bélanger-Chabot、Frédéric-Georges Fontaine

  DOI：10.1016/j.poly.2015.07.037

  日期：2016.3

  on the chemistry of phospholyl and boratabenzene complexes of zirconium, which have shown potential notably as polymerization catalysts, this study aims at exploring the synthesis of mono boratabenzene and mono phospholyl zirconium complexes and at studying their reactivity towards the formation of mixed (boratabenzene)(phospholyl)zirconium complexes. Several derivatives of (η5-phospholyl)Zr(NMe2)xCl3−x

  摘要为了扩展对锆的磷酰和硼酸苯络合物的化学反应的认识，已显示出潜在的聚合催化剂的作用，本研究旨在探索单硼酸苯和单磷酰锆络合物的合成，并研究它们对锆的反应性。混合形成（硼酸苯）（磷酰基）锆配合物。合成了（η5-磷酰基）Zr（NMe2）xCl3-x和（η6-硼根苯-NMe2）Zr（NMe2）xCl3-x的几种衍生物，并用作形成混合的（硼烷基苯）（磷酰基）锆络合物的前体。
• Generation and Trapping of a 1,1‘-Diphosphazirconocene
  作者：François-Xavier Buzin、François Nief、Louis Ricard、François Mathey

  DOI：10.1021/om010634u

  日期：2002.1.1

  The reduction of [(eta(5)-C4Me4P)(2)ZrCl2] (1) by magnesium in THF affords a transient octamethyl-1,1'-diphosphazirconocene which can be trapped by CO, bis(trimethylsilyl)acetylene, and 2-butyne to give the corresponding dicarbonyl 2, zirconacyclopropene 3, and zirconacyclopentadiene 4; all of these products have been characterized by X-ray analyses. An assessment of the,pi-basicity of the eta(5)-C4Me4P ligand has been made by several methods: (a) a comparison of the IR carbonyl stretching frequencies of 2 and of other dicarbonylzirconocene complexes, (b) a correlation of the C-13 NMR and IR data in 3 and in similar zirconacyclopropenes, and (c) an electrochemical study on 1. All these experiments confirm that the eta(5)-C4Me4P ligand is a poorer pi-base than the Cp ligand.