bis(p-methoxy-phenyl-imino-diphenylphosphoranyl)methane | 33535-75-0

• 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: bis(p-methoxy-phenyl-imino-diphenylphosphoranyl)methane
• 英文别名: bis(N-p-anisyliminodiphenylphosphoranyl)methane；(4-methoxyphenyl)imino-[[(4-methoxyphenyl)imino-diphenyl-λ5-phosphanyl]methyl]-diphenyl-λ5-phosphane
• CAS: 33535-75-0
• 化学式: C₃₉H₃₆N₂O₂P₂
• 分子量: 626.675
• InChiKey: UPAXPTFWVSYGDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.33
• 重原子数：
  45.0
• 可旋转键数：
  10.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  43.18
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  bis(p-methoxy-phenyl-imino-diphenylphosphoranyl)methane 在 PdCl₂(RCN)2 作用下， 以 not given 为溶剂， 生成 [PdCl2(CH(PPh2=NC6H4-4-OMe)(PPh2-N'H-C6H4-4-OMe))-C,N]
  参考文献：
  名称：

  Reactions of bis(iminophosphoranes) with palladium(II) dichloride: Metal-induced tautomerization orthopalladation and unexpected platinum-assisted [2 + 2] cycloaddition of an aryl-nitrile with a phosphinimine moiety

  摘要：

  Reactions of bis(iminophosphoranyl)methane, CH2(PPh(2)=N-aryl)(2), (BIPM; 1a, b) or 1, 1-bis(iminophosphoranyl)ethane (1, 1-BIPE; Ic) with Pd- and Pt-dichlorides containing weakly coordinating ligands (L) such as nitriles or cyclo-octadiene, afforded several products depending on the reaction time, type of ligand (la-c) or nature of the metal. The first reaction observed is a metal-assisted tautomerization of BIPM to aryl-N=PPh(2)-CH=PPh(2)-NH-aryl. When BIPM reacts with PdCl2(L)(2), exclusive formation of the C, N-chelate PdCl2{CH(PPh(2)=N-aryl)(PPh(2)-NH-aryl)} (2a, b) is observed, whereas with 1, 1-BIPE(1c) a product mixture consisting of a C, N-chelate (2c) and an N, N'-chelate (3) is found. Orthometallation of the four-membered palladacycle (2) took place upon heating, giving the five-membered palladacycle [PdCl2(2-C6H4-PPh(NHI-pTol)-C'H-PPh(2)(NH-pTol)}-C, C'] (4). The molecular structure of 4 has been determined by X-ray crystallography, Reactions of BIPM (1a, b) with PtCl2(RC=N)(2) (R = phenyl, p-tolyl) afforded entirely different products: the six-membered platinacycles [PtCl(RC=N){aryl-N=C(R)-N=PPh(2)-CH=PPb2-NH-aryl}-C, N]Cl (5) and [PtCl2{aryl-N=C(R)-N=PPh(2)-CH=PPh(2)-NH-aryl}-C, N] (6), due to an unexpected 2 + 2 cycloaddition of a nitrile with a P=N group.

  DOI：

  10.1016/s0022-328x(96)06684-3
• 作为产物：
  描述：

  1-叠氮基-4-甲氧基苯 、 双二苯基膦甲烷 以 苯 为溶剂， 以90%的产率得到bis(p-methoxy-phenyl-imino-diphenylphosphoranyl)methane
  参考文献：
  名称：

  Imhoff, P.; van Asselt, R.; Elsevier, C. J., Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 47, p. 401 - 415

  摘要：

  DOI：

文献信息

• Reactions of bis(iminophosphoranyl)methanes with chloro-bridged rhodium or iridium dimers giving complexes in which the ligand is coordinated either as a σ-N,σ-N′ or as a σ-N, σ-C chelate. X-ray crystal structure of the σ-N, σ-N′ Rh(I) complex Rh{(4-CH3-C6H4-NPPh2)2CH2}(COD)]PF6
  作者：Pieter Imhoff、Rob van Asselt、Cornelis J. Elsevier、Martin C. Zoutberg、Casper H. Stam

  DOI：10.1016/s0020-1693(00)83048-0

  日期：1991.6

  observed reflections converged to R = 0.087. The structure comprises a distorted square planar Rh(I) environment where the coordination positions are taken by COD and the two nitrogen atoms of the bipm ligand. The six-membered RhNPCPNRh metallacycle has a distorted boat conformation. Synthesis and spectroscopic data of the pure complexes II and III are described. The formation of the complexes and

  [ML 2 CI] 2（MRh，Ir; L 2COD，NBD;LCO）与双亚氨基磷酰基甲烷CH 2（PPh 2NR）2（bipm，I）的桥拆分反应导致具有N，N'和N，C二齿配位bipm的Rh（I）和Ir（I）络合物：[ML 2 （4-R'-C 6 H 4-NPPh2）2 CH 2}] + X-（II）和[ML 2 （4-R'- C 6 H 4 -NH-PPh 2）CH（PPh 2NC6 H 4 -R'-4）}] + X-（III; R′＝ CH 3，NO 2 OCH 3； X ＝ Cl，MCl 2 L 2，BF 4，PF 6）。II：III的比例取决于金属，bipm配体I，溶剂和银（I）或钠盐的存在。在N，C配位的bipm中，发生了从碳到侧氮原子的1,3-H互变异构转变。解析了[Rh （4-CH 3 -C 6 H 4 -N 2PPh 2）2 CH 2}（COD）] PF
• Selective Formation of Four-Membered Metallacyclic Pt-N-P-C Compounds from Reactions of Bis((N-arylimino)phosphoranyl)methanes with Halide-Bridged Platinum(II) Phosphine Dimers. X-ray Crystal Structures of [PtCl(PMe2Ph){CH(PPh2:NC6H4-4-CH3)(PPh2N'HC6H4-4-CH3)}]+Cl- and [PtCl(PEt3){CH(PPh2:NC6H4-4-CH3)(PPh2N'HC6H4-4-CH3)}]+[PtCl3(PEt3)]-
  作者：Mandy W. Avis、Kees Vrieze、Huub Kooijman、Nora Veldman、Anthony L. Spek、Cornelis J. Elsevier

  DOI：10.1021/ic00120a013

  日期：1995.8

  Bridge-splitting reactions of Pt(2)X(4)(PR(3))(2) (X = Cl, Br; PR(3) = PEt(3), PMe(2)Ph) with bis(iminophosphoranyl)methanes CH2(PPh(2)=NC6H4-4-R')(2) (BIPM: 1a, R' = Me; 1b, R' = OMe) produced Pt(II) complexes, in which the BIPM ligand is N,C-coordinated: [PtX(PR(3))CH-(PPh(2)=N-C6H4-4-R') (PPh(2)-NH-C6H4-4-R')}]Y-+(-) (2a-f, R' = CH3, OCH3, Y = Cl, Br, BF4, CF3CO2; 2g, R' = CH3, PR(3) = PEt(3), Y = PtCl(3)PEt(3)). In the N,C-coordinated BIPM, a net 1,3-H-shift from the bridging methylene group to the noncoordinated N-atom has taken place. NMR studies have revealed a monodentate sigma-N-coordinated species PtX(2)(PR(3))N(C6H4-4-R')=PPh(2)CH(2)PPh(2)=NC6H4 A, as the first intermediate in the formation of 2. The complex formation is strongly dependent on the metal to ligand ratio, M:L. For M:L = 2:1, compound 2g(i) was formed, a N,N'-coordinated six-membered platinacycle, followed by conversion into the N,C chelate 2g, whereas at M:L = 1:2 two new products were obtained; a deprotonated Pt(II) complex with N,C-coordinated BIPM, [PtX(PR(3))CH(PPh(2)=NC6H4-4-R')(2)] (3; X = Cl, PR(3) = PEt(3), R' = CH3), and the HCl salt of the ligand [HC(PPh(2)NHC(6)H(4)-4-R')(2)]Cl-+(-) (4). The molecular structures of [PtCl(PMe(2)Ph)CH(PPh(2)=NC6H4-4-CH3)(PPh(2)N'HC6H4-4-CH3)}](+)(Cl)(-) (2d) and [PtCl(PEt(3))CH(PPh(2)=NC6H4-4-CH3)(PPh(2)N'HC6H4-4-CH3)}](+)(PtCl(3)PEt(3))(-) (2g) have been determined by X-ray crystallography. Crystal data for 2d: trigonal, space group P $($) over bar$$ 1, with a = 14.3852(11) Angstrom, b = 15.4886(9) Angstrom, c = 20.190(2) Angstrom, alpha = 100.580(7)degrees, beta = 92.223(8)degrees, gamma = 99.508(6)degrees, V = 4350.1(6) Angstrom(3), and Z = 4. Crystal data for 2g: trigonal, space group Pi, with a = 10.1970(8) Angstrom, b = 14.5045(9) Angstrom, c = 20.5471(19) Angstrom, alpha = 96.154(7)degrees, beta = 103.993(7)degrees, gamma 107.548(6)degrees, V = 2757.8(4) Angstrom(3), and Z = 2. The structure refinement converged to R(w) = 0.0432, R = 0.0436 for 2d and wR2 = 0.1247, R1 = 0.501 for 2g. The structure of the cationic parts of 2d and 2g comprises a distorted square planar Pt(II) environment, the coordination sites taken by PR(3), Cl, and the N and C atoms of the BIPM ligand. The structure of the anionic part of 2g, PtCl3(PEt(3)), is almost perfectly square-planar and is linked with the cationic part via a NH...Cl hydrogen bond.