(di-tert-butylphosphino)(dicyclohexylphosphino)methane | 185537-55-7

• 物质功能分类: 有机原料 - 有机膦化合物
• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: (di-tert-butylphosphino)(dicyclohexylphosphino)methane
• 英文别名: dicyclohexylphosphino di-tert-butylphosphinomethane；Bu^t2PCH2PCy2；ctbpm；Phosphine, [[bis(1,1-dimethylethyl)phosphino]methyl]dicyclohexyl-；ditert-butyl(dicyclohexylphosphanylmethyl)phosphane
• CAS: 185537-55-7
• 化学式: C₂₁H₄₂P₂
• 分子量: 356.512
• InChiKey: GABREVZSSDFGFD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (di-tert-butylphosphino)(dicyclohexylphosphino)methane 以 乙醚 、 乙醇 为溶剂， 生成 [(t-Bu2PCH2P(C6H11)2-κ2P)Ni(η3-benzyl)][B(3,5-(CF3)2C6H3)4]
  参考文献：
  名称：

  Crowded Diphosphinomethane Ligands in Catalysis: [(R₂PCH₂PR′₂-κ²P)NiR″]⁺Cations for Ethylene Polymerization without Activators

  摘要：

  The preparation of a series of nickel dichloride complexes with bulky diphosphinomethane chelate ligands R2PCH2PR'(2) is reported. Reaction with the appropriate Grignard reagent leads to the corresponding dimethyl and dibenzyl complexes. Cationic monomethyl and mono-eta(3)-benzyl complexes are generated from these dialkyl complexes by protonation with [H(OEt2)(2)](+)[B(3,5-(CF3)(2)C6H3)(4)](-), while the complex [(dtbpm-K2P)Ni(eta(3)-CH(CH2Ph)Ph](+)[B(3,5-(CF3)(2)C6H3)(4)](-) is obtained from protonation of the Ni(0) olefin complex (dtbpm-kappa P-2)Ni(eta(2)-trans-stilbene). Crystal structures of examples of dichlorides, dimethyl, dibenzyl, cationic methyl, and cationic eta(3)-benzyl complexes are reported. Solutions of the cations polymerize ethylene under mild conditions and without the necessity of an activating agent, to form polyethylene having high molecular weights and low degrees of chain branching. In comparison to the Ni methyl cations, the eta(3)-benzyl cation complexes are more stable and somewhat less active but still very efficient in C2H4 polymerization. The effect on the resulting polyethylene of varying the substituents R, R' on the phosphine ligand has been examined, and a dear trend for longer chain PE with less branching in the presence of more bulky substituents on the diphosphine has been found. Density functional calculations have been used to examine the rapid suprafacial eta(3) to eta(3) haptotropic shift processes of the [(R2PCH2PR'(2))Ni] fragment and the eta(3)-eta(1) change of the coordination mode of the benzyl group required for polymerization in those cations.

  DOI：

  10.1021/om200715w
• 作为产物：
  描述：

  氯代环己烷 在 叔丁基锂 、 magnesium 、 三氯化磷 作用下， 以 四氢呋喃 、 乙醚 、 正庚烷 、 正戊烷 为溶剂， 反应 2.5h， 生成 (di-tert-butylphosphino)(dicyclohexylphosphino)methane
  参考文献：
  名称：

  立体拥挤的二膦甲烷配体：t Bu 2 PCH 2 P t Bu 2及其相关物种的分子结构，紫外光电子能谱和常规合成

  摘要：

  一系列的高度拥挤对称和不对称diphosphinomethanes - [R 2 PCH 2 PR' 2，重要配体在过渡金属化学和催化方面，即t Bu 2 PCH 2 P t Bu 2 （dtbpm，1），Cy 2 PCH 2 PCy 2 （dcpm，2），t Bu 2 PCH 2 PCy 2 （ctbpm，3），t Bu 2 PCH 2 P i Pr 2 （iptbpm，4）和t Bu 2 PCH 2 PPh 2 （ptbpm，5），已使用一般便捷的路线以高收率制备，详细说明请参见1。除4是无色液体外，这些化合物在室温下为结晶固体。它们的分子结构已经通过单晶X射线衍射以及更高的同系物1，t Bu 2 CH 2 CH 2 t Bu 2 （dtbpe，6）进行了测定。的氧化钛的固态结构1，吨卜2 P（O）CH 2 P（O）吨卜2 （7），和两个phospho阳离子衍生自1的质子化[ t Bu

  DOI：

  10.1039/b210114a

文献信息

• Intermolecular Hydroacylation: High Activity Rhodium Catalysts Containing Small-Bite-Angle Diphosphine Ligands
  作者：Adrian B. Chaplin、Joel F. Hooper、Andrew S. Weller、Michael C. Willis

  DOI：10.1021/ja211649a

  日期：2012.3.14

  rhodium complexes containing methylene bridged diphosphine ligands, viz. [Rh(C(6)H(5)F)(R(2)PCH(2)PR'(2))][BAr(F)(4)] (R, R' = (t)Bu or Cy; Ar(F) = C(6)H(3)-3,5-(CF(3))(2)), are shown to be practical and very efficient precatalysts for the intermolecular hydroacylation of a wide variety of unactivated alkenes and alkynes with β-S-substituted aldehydes. Intermediate acyl hydride complexes [Rh((t)Bu(2)PCH

  含有亚甲基桥联二膦配体的易于制备且可长期稳定的铑配合物，即。[Rh(C(6)H(5)F)(R(2)PCH(2)PR'(2))][BAr(F)(4)] (R, R' = (t)Bu 或 Cy ; Ar(F) = C(6)H(3)-3,5-(CF(3))(2))，被证明是一种实用且非常有效的预催化剂，可用于多种未活化烯烃的分子间加氢酰化和带有 β-S-取代醛的炔烃。中间酰基氢化物复合物 [Rh((t)Bu(2)PCH(2)P(t)Bu(2))Hκ(2)(S,C)-SMe(C(6)H(4)CO )}(L)](+)（L = 丙酮、MeCN、[NCCH(2)BF(3)](-)）和脱羰产物 [Rh((t)Bu(2)PCH(2)P( t)Bu(2))(CO)(SMePh)](+) 已在溶液中并通过 X 射线晶体学从使用 2-(甲硫基) 苯甲醛的化学计量反应中表征。还报道了与膦 2-(二苯基膦基)苯甲醛
• Wolf, Justin; Manger, Matthias; Schmidt, Ulrich, Journal of the Chemical Society, Dalton Transactions, 1999, # 11, p. 1867 - 1875
  作者：Wolf, Justin、Manger, Matthias、Schmidt, Ulrich、Fries, Guido、Barth, Dietmar、Weberndoerfer, Birgit、Vicic, David A.、Jones, William D.、Werner, Helmut

  DOI：——

  日期：——
• US5891989A
  申请人：——

  公开号：US5891989A

  公开（公告）日：1999-04-06
• US6031057A
  申请人：——

  公开号：US6031057A

  公开（公告）日：2000-02-29
• Crowded Diphosphinomethane Ligands in Catalysis: [(R₂PCH₂PR′₂-κ²<i>P</i>)NiR″]^<b>+</b>Cations for Ethylene Polymerization without Activators
  作者：Madeleine Schultz、Frank Eisenträger、Christian Regius、Frank Rominger、Patrick Hanno-Igels、Paul Jakob、Irene Gruber、Peter Hofmann

  DOI：10.1021/om200715w

  日期：2012.1.9

  The preparation of a series of nickel dichloride complexes with bulky diphosphinomethane chelate ligands R2PCH2PR'(2) is reported. Reaction with the appropriate Grignard reagent leads to the corresponding dimethyl and dibenzyl complexes. Cationic monomethyl and mono-eta(3)-benzyl complexes are generated from these dialkyl complexes by protonation with [H(OEt2)(2)](+)[B(3,5-(CF3)(2)C6H3)(4)](-), while the complex [(dtbpm-K2P)Ni(eta(3)-CH(CH2Ph)Ph](+)[B(3,5-(CF3)(2)C6H3)(4)](-) is obtained from protonation of the Ni(0) olefin complex (dtbpm-kappa P-2)Ni(eta(2)-trans-stilbene). Crystal structures of examples of dichlorides, dimethyl, dibenzyl, cationic methyl, and cationic eta(3)-benzyl complexes are reported. Solutions of the cations polymerize ethylene under mild conditions and without the necessity of an activating agent, to form polyethylene having high molecular weights and low degrees of chain branching. In comparison to the Ni methyl cations, the eta(3)-benzyl cation complexes are more stable and somewhat less active but still very efficient in C2H4 polymerization. The effect on the resulting polyethylene of varying the substituents R, R' on the phosphine ligand has been examined, and a dear trend for longer chain PE with less branching in the presence of more bulky substituents on the diphosphine has been found. Density functional calculations have been used to examine the rapid suprafacial eta(3) to eta(3) haptotropic shift processes of the [(R2PCH2PR'(2))Ni] fragment and the eta(3)-eta(1) change of the coordination mode of the benzyl group required for polymerization in those cations.