zirconocene(P(2,6-Mes2C6H3))P(CH3)3 | 252557-68-9

• 英文名称: zirconocene(P(2,6-Mes2C6H3))P(CH3)3
• 英文别名: Cl2Zr=P[2,6-Mes2C6H3](P(CH3)3)；Cl2Zr=P[DMP](P(CH3)3)
• CAS: 252557-68-9
• 化学式: C₃₇H₄₄P₂Zr
• 分子量: 641.928
• InChiKey: HFFXCJXMLYKXDR-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

• 作为反应物：
  描述：

  zirconocene(P(2,6-Mes2C6H3))P(CH3)3 、 二苯基氯化膦 以 苯 为溶剂， 以0%的产率得到
  参考文献：
  名称：

  Triphosphane formation from the terminal zirconium phosphinidene complex [Cp2ZrPDmp(PMe3)] (Dmp=2,6-Mes2C6H3) and crystal structure of DmpP(PPh2)2

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(01)00863-4
• 作为产物：
  描述：

  zirconocene(P(H)(2,6-Mes2C6H3))2 、 三甲基膦 以 四氢呋喃 为溶剂， 生成 zirconocene(P(2,6-Mes2C6H3))P(CH3)3
  参考文献：
  名称：

  Sterically promoted zirconium–phosphorus π-bonding: structural investigations of [Cp2Zr(Cl){P(H)Dmp}] and [Cp2Zr{P(H)Dmp}2] (Dmp=2,6-Mes2C6H3)

  摘要：

  The new terminal zirconocene-organophosphanido complexes [Cp2Zr(Cl){P(H)Dmp}] (1) and [Cp2Zr{P(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 [Cp2Zr{P(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.

  DOI：

  10.1016/s0020-1693(99)00335-7

文献信息

• Phosphinidene Complexes of Scandium: Powerful PAr Group-Transfer Vehicles to Organic and Inorganic Substrates
  作者：Benjamin F. Wicker、Jennifer Scott、José G. Andino、Xinfeng Gao、Hyunsoo Park、Maren Pink、Daniel J. Mindiola

  DOI：10.1021/ja100214e

  日期：2010.3.24

  The first phosphinidene complexes of scandium are reported in this contribution. When complex (PNP)Sc(CH3)Br (1) is treated with 1 equiv of LiPH[Trip] (Trip = 2,4,6-(Pr3C6H2)-Pr-i), the dinuclear scandium phosphinidene complex [(PNP)Sc(mu(2)-P[Trip])](2) (2) is obtained. However, treating 1 with a bulkier primary phosphide produces the mononuclear scandium ate complex [(PNP)Sc(mu(2)-P[DMP](mu(2)-Br)Li] (3) (DMP = 2,6-Mes(2)C(6)H(3)). The Li cation in 3 can be partially encapsulated with DME to furnish a phosphinidene salt derivative, (PNP)Sc(mu(2)-P[DMP])(mu(2)-Br)Li(DME)] (4). We also demonstrate that complex 3 can readily deliver the phosphinidene ligand to organic substrates such as OCPh2 and Cl(2)PMes* as well as inorganic fragments such as Cp2ZrCl2, Cp*2TiCl2, and Cp2TiCl2 in the presence of P(CH3)(3). Complexes 2-4 have been fully characterized, including single crystal X-ray diffraction and DFT Studies.