dichlorosilylene*dinitrogen complex | 625456-23-7

• 英文名称: dichlorosilylene*dinitrogen complex
• CAS: 625456-23-7
• 化学式: Cl₂Si*N₂
• 分子量: 127.005
• InChiKey: MFWLIDRCUSVXJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.03
• 重原子数：
  5.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  47.58
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  氮 、 六氯乙硅烷 以 neat (no solvent, gas phase) 为溶剂， 生成 dichlorosilylene*dinitrogen complex
  参考文献：
  名称：

  摘要：

  Interaction of dichlorosilylene with dinitrogen in mixed Ar-N-2 matrices at 9 - 10 K was studied by IR spectroscopy. A donor-acceptor complex Cl2Si (.) N-2 was found and characterized by six bands of symmetric (at 511.2, 508.9, and 506.5 cm(-1)) and antisymmetric (at 500.1, 496.9, and 495.1 cm-1) stretching vibrations of Si-Cl bonds in the most abundant isotopomers. Two bands at 498.7 and 493.5 cm(-1) observed in mixed matrices were tentatively assigned to Cl2Si (.) (N-2)(2) complex. Several stretching vibration bands of minor isotopomers of SiCl2) were detected for the first time in argon matrices. Assignment has been done for the isotopic structure of SiCl2 associates with dinitrogen observed in N-2 matrices. Dimerization of SiCl2 and its complexation with one and two N-2 molecules were studied by quantum-chemical DFT calculations (PBE and B3LYP functionals). The structures, energies, and vibrational frequencies of the Cl2Si (.) N-2 and Cl2Si (.) (N-2)(2) complexes and the Si2Cl4 dimer were determined. The energies of SiCl2 complexation with one and two N2 molecules obtained from PBE and B3LYP calculations are 0.3 and 0.6 kcal mol(-1), respectively. More accurate G2(MP2,SVP) calculations using the B3LYP geometries have predicted a higher stability of the Cl2Si (.) N-2 complex (1.2 kcal mol(-1)). The calculated and experimental vibrational frequencies of reagents and complexes are in good agreement. A correlation has been established between the PBE calculated energies of complexation of EHal(2) (E = Si, Ge, Sri, Pb) with N-2 and the experimentally observed shifts of E-Hal stretching vibrations in EHal(2) upon complexation. The strength of the complexes with N-2 increases on going from dihalosilylenes to dihaloplumbylenes.

  DOI：

  10.1023/a:1023973815486