[PtCl(PEt3)(CH2(PPh2=NC6H4-4-Me)2)-N,N'](+)[PtCl3(PEt3)](-) | 167895-79-6

• 英文名称: [PtCl(PEt3)(CH2(PPh2=NC6H4-4-Me)2)-N,N'](+)[PtCl3(PEt3)](-)
• CAS: 167895-79-6
• 化学式: C₆H₁₅Cl₃PPt*C₄₅H₅₁ClN₂P₃Pt
• 分子量: 1362.97
• InChiKey: UNZYGHHYUMRZTC-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [PtCl(PEt3)(CH2(PPh2=NC6H4-4-Me)2)-N,N'](+)[PtCl3(PEt3)](-) 以 甲苯 为溶剂， 生成 [PtCl(PEt3)(CH(PPh2=NC6H4-4-Me)(PPh2N'HC6H4-4-Me))-C,N](+)[PtCl3(PEt3)](-)
  参考文献：
  名称：

  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)]-

  摘要：

  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.

  DOI：

  10.1021/ic00120a013
• 作为产物：
  描述：

  di-μ-chloro-bis[chloro(triethylphosphine)platinum(II)] 、 bis(N-p-tolyliminodiphenylphosphoranyl)methane 以 甲苯 为溶剂， 以96%的产率得到[PtCl(PEt3)(CH2(PPh2=NC6H4-4-Me)2)-N,N'](+)[PtCl3(PEt3)](-)
  参考文献：
  名称：

  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)]-

  摘要：

  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.

  DOI：

  10.1021/ic00120a013