Methyl-(4-methylphenyl)imino-diphenyl-lambda5-phosphane | 133752-61-1

• 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: Methyl-(4-methylphenyl)imino-diphenyl-lambda5-phosphane
• 英文别名: methyl-(4-methylphenyl)imino-diphenyl-λ5-phosphane
• CAS: 133752-61-1
• 化学式: C₂₀H₂₀NP
• 分子量: 305.359
• InChiKey: GUJJROOKBIWQDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Methyl-(4-methylphenyl)imino-diphenyl-lambda5-phosphane 在 n-butyl lithium 、 HCl 作用下， 以 乙醚 、 苯 为溶剂， 生成
  参考文献：
  名称：

  Stabilization of rhodium(I)- and iridium(I)-alkyl bonds by intramolecular coordination of an iminophosphorane. X-ray crystal structure of [Rh(CH2PPh2:NC6H4CH3-4)(COD)]

  摘要：

  Lithium(iminophosphoranyl)methanide Li[CH2PPh2 = N-C6H4-CH3-4] (2a) reacts with the rhodium and iridium complexes [ML2Cl]2 (M = Rh, L2 = COD, L = CO: M = Ir, L2 = COD) to yield the complexes [M(CH2PPh2 = N-C6H4-CH3-4)L2] (3a, M = Rh, L2 = COD; 3c, M = Rh, L = CO; 3e, M = Ir, L2 = COD), in which the (iminophosphoranyl)methanide ligand is coordinated as a sigma-N,sigma-C chelate, forming a new four-membered metallacycle. The molecular structure of 3a has been determined by X-ray crystallographic analysis. Compound 3a crystallizes in space group P2(1)/n with a = 31.877 (3) angstrom, b = 12.932 (2) angstrom, c = 13.579 (2) angstrom, and beta = 99.14 (1)-degrees, and the structure was refined to R = 0.041 (R(W) = 0.043) by using 10 500 independently measured reflections. The square-planar coordination around rhodium (I) involves the two olefinic bonds of COD and the N and C atoms of the sigma-N,sigma-C chelated (iminophosphoranyl)methanide ligand (Rh-N = 2.132 (3) angstrom and Rh-C1 = 2.128 (3) angstrom). In the rhodium and iridium (iminophosphoranyl)methanide complexes the M-C(sp3) bond is effectively stabilized by intramolecular coordination of an iminophosphorane group, as illustrated by their thermal stability and the inertness of 3a,c toward small molecules such as CO and CO2, as well as activated olefins and acetylenes. Reactions of the rhodium complexes 3a,c with 1 equivalent of HCl gives either the sigma-N-coordinated iminophosphorane complex [Rh(4-CH3-C6H4-N = P(CH3)Ph2)L2Cl] (5) or the N-protonated species [Rh(CH2PPh2NH-C6H4-CH3-4)L2]Cl (6) depending on the ligand L and the applied conditions. The reaction proceeds most probably via an intermediate Rh(III) oxidative-addition product (a metal hydride was observed by IR spectroscopy) that further reacts via hydrogen migration reactions to yield 5 or 6, i.e. with a net protonation of the C atom or the N atom, respectively, in 3.

  DOI：

  10.1021/om00051a038

文献信息

• Iminophosphorane complexes of rhodium(I) and X-ray crystal structure of [Rh(COD)Cl(Et3PN-p-tolyl)]
  作者：P. Imhoff、C.J. Elsevier、C.H. Stam

  DOI：10.1016/s0020-1693(00)84829-x

  日期：1990.9
• Stabilization of rhodium(I)- and iridium(I)-alkyl bonds by intramolecular coordination of an iminophosphorane. X-ray crystal structure of [Rh(CH2PPh2:NC6H4CH3-4)(COD)]
  作者：Pieter Imhoff、Sylvia C. A. Nefkens、Cornelis Elsevier、Kees Goubitz、Caspar H. Stam

  DOI：10.1021/om00051a038

  日期：1991.5

  Lithium(iminophosphoranyl)methanide Li[CH2PPh2 = N-C6H4-CH3-4] (2a) reacts with the rhodium and iridium complexes [ML2Cl]2 (M = Rh, L2 = COD, L = CO: M = Ir, L2 = COD) to yield the complexes [M(CH2PPh2 = N-C6H4-CH3-4)L2] (3a, M = Rh, L2 = COD; 3c, M = Rh, L = CO; 3e, M = Ir, L2 = COD), in which the (iminophosphoranyl)methanide ligand is coordinated as a sigma-N,sigma-C chelate, forming a new four-membered metallacycle. The molecular structure of 3a has been determined by X-ray crystallographic analysis. Compound 3a crystallizes in space group P2(1)/n with a = 31.877 (3) angstrom, b = 12.932 (2) angstrom, c = 13.579 (2) angstrom, and beta = 99.14 (1)-degrees, and the structure was refined to R = 0.041 (R(W) = 0.043) by using 10 500 independently measured reflections. The square-planar coordination around rhodium (I) involves the two olefinic bonds of COD and the N and C atoms of the sigma-N,sigma-C chelated (iminophosphoranyl)methanide ligand (Rh-N = 2.132 (3) angstrom and Rh-C1 = 2.128 (3) angstrom). In the rhodium and iridium (iminophosphoranyl)methanide complexes the M-C(sp3) bond is effectively stabilized by intramolecular coordination of an iminophosphorane group, as illustrated by their thermal stability and the inertness of 3a,c toward small molecules such as CO and CO2, as well as activated olefins and acetylenes. Reactions of the rhodium complexes 3a,c with 1 equivalent of HCl gives either the sigma-N-coordinated iminophosphorane complex [Rh(4-CH3-C6H4-N = P(CH3)Ph2)L2Cl] (5) or the N-protonated species [Rh(CH2PPh2NH-C6H4-CH3-4)L2]Cl (6) depending on the ligand L and the applied conditions. The reaction proceeds most probably via an intermediate Rh(III) oxidative-addition product (a metal hydride was observed by IR spectroscopy) that further reacts via hydrogen migration reactions to yield 5 or 6, i.e. with a net protonation of the C atom or the N atom, respectively, in 3.