lithium 2,6-dimesitylphenylphosphide-diethyl ether | 478622-13-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: lithium 2,6-dimesitylphenylphosphide-diethyl ether
• 英文别名: Li(P(H)(2,6-Mes2C6H3))*Et2O
• CAS: 478622-13-8；260998-02-5
• 化学式: C₄H₁₀O*C₂₄H₂₆P*Li
• 分子量: 426.508
• InChiKey: WWTHRXYCCKRGHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.69
• 重原子数：
  31.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  lithium 2,6-dimesitylphenylphosphide-diethyl ether 、 [(dtbpe)Ni(μ-Cl)]₂ 以 二氯甲烷 为溶剂， 以93%的产率得到[(1,2-bis(di-tert-butylphosphino)ethane)NiPH(2,6-dimesitylphenyl)]
  参考文献：
  名称：

  镍的单体磷化和磷化烯配合物

  摘要：

  包含螯合 1,2-双（二叔丁基膦）乙烷 (dtbpe) 配体和末端 PR(2)（ -) 或 PR(2-) 配体已经制备。配合物 (dtbpe)Ni[P(t-Bu)(2)] (2), [(dtbpe)Ni[=P(t-Bu)(2)](+)][PF(6)(-) ] (3), [(dtbpe)Ni[=P(H)(dmp)](+)][PF(6)(-)] (5), 和 (dtbpe)Ni[=P(dmp)] ( 6) 已通过单晶 X 射线衍射方法进行结构表征。三配位 d(8) 配合物表现出 Ni-P 键长和配体几何形状，表明它们参与了对称允许的配体与金属 pi 键合，涉及磷 p 电子和位于Ni协调平面。化合物 6 是后过渡金属末端膦叉化合物的罕见例子。

  DOI：

  10.1021/ja017787t

文献信息

• Synthesis, structure, and reactivity of platinum compounds featuring terminal amido and phosphido ligands
  作者：Rory Waterman、Daniel J. Mindiola、Christopher R. Clough、Gregory L. Hillhouse

  DOI：10.1016/j.ica.2014.07.038

  日期：2014.10

  dmp = 2,6-dimesitylphenyl, Mes∗ = 2,4,6-tri-tert-butylphenyl). Both families of compounds resist attempts to deprotonate the amido or phosphido ligand with either external bases or through alkane or arene elimination. Compound 11 reacts with various acids to afford salts having the cation [(dtbpe)PtMe(PH2Mes∗)]+ [12]+. Compounds 6, 9·0.5Et2O, 10·Et2O, 11·Et2O, and the salt [12][BArf4] were structurally

  摘要使用空间受限的1,2-双（二叔丁基膦基）乙烷（dtbpe）配体，形成了一般形式（dtbpe）PtX（NHAr）的末端苯胺基化合物家族（X = Cl，2; Me，6 ;（Ph，7; Ar = 2,6-二异丙基苯基）以及（dtbpe）Pt（NHPh）2（8）是通过使用（dtbpe）PtCl2进行盐复分解以高分离产率制备的。同样，制备了新的立体式末端磷酸酯化合物，其通式为（dtbpe）PtX（PHAr）（X / Ar = Cl / dmp，9; Cl / Mes ∗，10; Me / Mes ∗，11;其中dmp = 2 ，6-二甲苯基苯基，Mes ＝ 2,4,6-三叔丁基苯基）。这两类化合物都可以抵抗用外部碱基或通过烷烃或芳烃消除使酰胺或磷配体去质子化的尝试。化合物11与各种酸反应，得到具有阳离子[（dtbpe）PtMe（PH2Mes ∗）] + [12] +的盐。化合物6、9·0.5Et2O，10·Et2O，
• Triphosphane formation from the terminal zirconium phosphinidene complex [Cp2ZrPDmp(PMe3)] (Dmp=2,6-Mes2C6H3) and crystal structure of DmpP(PPh2)2
  作者：Eugenijus Urnezius、Kin-Chung Lam、Arnold L. Rheingold、John D. Protasiewicz

  DOI：10.1016/s0022-328x(01)00863-4

  日期：2001.7

  The new terminal phosphinidene complex [Cp2Zr=PDmp(PMe3)] (Dmp = 2,6-Mes(2)C(6)H(3); 1) was prepared in 81% yield by the reaction of [Li(Et2O)][P(H)Dmp] with [Cp2Zr(Me)Cl] in the presence of excess PMe3. Compound 1 reacts with Ph2PCl to produce selectively the sterically congested triphosphane DmpP(PPh2)(2) (2) and [Cp2ZrCl2] in high yields. The structure of 2 obtained by X-ray diffraction analysis of a single crystal reveals phosphorus-phosphorus bond lengths of 2.251(2) and 2.234(2) Angstrom and a PPP bond angle of 105.46(6)degrees. (C) 2001 Elsevier Science B.V. All rights reserved.
• Sterically promoted zirconium–phosphorus π-bonding: structural investigations of [Cp2Zr(Cl){P(H)Dmp}] and [Cp2Zr{P(H)Dmp}2] (Dmp=2,6-Mes2C6H3)
  作者：Eugenijus Urn≐žius、Stephen J. Klippenstein、John D. Protasiewicz

  DOI：10.1016/s0020-1693(99)00335-7

  日期：2000.1

  The new terminal zirconocene-organophosphanido complexes [Cp2Zr(Cl)P(H)Dmp}] (1) and [Cp2ZrP(H)Dmp}(2)] (2) (Dmp = 2,6-Mes(2)C(6)H(3)) bearing the sterically demanding ligand Dmp have been prepared and structurally characterized. A flattened pyramidal geometry for the phosphorus atom of 1 and a shortened Zr-P bond length of 2.638(1) Angstrom provide evidence for moderate Zr-P pi-bonding. Compound 2, however, displays both pyramidal and planar phosphorus atoms. The corresponding Zr-P bond lengths of 2.726(2) and 2.519(2) Angstrom, in conjunction with the phosphorus geometries, indicate that one phosphanido ligand is engaged in substantial pi-bonding to the zirconium center while minimal, if any, of such interactions are present for the other phosphanido ligand. The solid state structures and P-31 NMR spectra for 1 and 2 are very different than previously reported [Cp(2)zr(Cl)P(H)Mes*}] and [Cp2ZrP(H)Mes*}(2)] (Mes* = 2,4,6-(Bu3C6H2)-Bu-t) which carry the related sterically demanding group Mes*. Comparisons to other structurally characterized zirconocene(IV) and hafnocene(IV) complexes having terminal phosphanido ligands suggest that upon increasing the steric congestion at the phosphorus atoms greater ir. interactions with the metal centers are afforded if such steric interactions do not prevent achieving proper alignment of the PR, group for optimal M-P pi-bonding. (C) 2000 Elsevier Science S.A. All rights reserved.