deuteroimine | 15117-75-6

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 均质其他非金属化合物
• 英文名称: deuteroimine
• CAS: 15117-75-6
• 化学式: H₂N
• 分子量: 17.0146
• InChiKey: MDFFNEOEWAXZRQ-MICDWDOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  1
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  氨 、 氘 以 neat (no solvent, gas phase) 为溶剂， 生成 deuteroimine
  参考文献：
  名称：

  The microwave spectrum of the NHD radical in the ground electronic state, 2A′′

  摘要：

  The microwave spectrum of the monodeuterated species of NH2, NHD(X̃ 2A′′), was observed in the millimeter- and submillimeter-wave region. The NHD radical was produced by a dc-glow discharge through a NH3 and D2 mixture at around 220 K. Ten rotational transitions with both b- and a-type selection rules were observed in the 177–517 GHz region. The most important rotational transitions for astronomical observations, 101–000 and 110–101, were included and their detailed fine and hyperfine components were measured with high precision. The hyperfine interaction of the nitrogen, hydrogen, and deuterium nuclei, which are similar in magnitude, caused complicated hyperfine patterns and made their assignment relatively difficult. A least-squares analysis of the measured frequencies resulted in the determination of 40 molecular constants including nuclear spin–rotation coupling constants of N, H, D and, furthermore, nonaxial components of magnetic dipolar terms of H and D. The necessity of a higher K-dependent term of the dipole–dipole interaction constant for the hydrogen nucleus relative to the principal axis system reflects the effective geometrical change of the rotational levels.

  DOI：

  10.1063/1.475224

文献信息

• The Four Isotopomer Reactions of NH(<i>a</i>) and ND(<i>a</i>) with NH₃(<i>X̃</i>) and ND₃(<i>X̃</i>)
  作者：L. Adam、W. Hack、Matthias Olzmann

  DOI：10.1524/zpch.218.4.439.29201

  日期：2004.4.1

  The reactions

  NH(a) + NH₃(X̃) → products (1)

  ND(a) + NH₃(X̃) → products (2)

  NH(a) + ND₃(X̃) → products (3)

  ND(a) + ND₃(X̃) → products (4)

  were studied in a quasi-static reaction cell at room temperature and pressures of 10 and 20mbar with He as the main carrier gas. The electronically excited reactants NH(a) and ND(a) were generated by laser-flash photolysis of HN₃ and DN₃, respectively, at λ = 308nm and detected by laser-induced fluorescence (LIF). Also the ground state species NH(X) and ND(X) as products were detected by LIF.

  From the measured concentration-time profiles of NH(a) and ND(a) under pseudo-first order conditions, the following rate constants were obtained:

  NH(a) + NH₃(X̃) → products (1)

  ND(a) + NH₃(X̃) → products (2)

  NH(a) + ND₃(X̃) → products (3)

  ND(a) + ND₃(X̃) → products (4)

  k ₁ = (9.1 ± 0.9) × 10¹³ cm³mol⁻¹s⁻¹

  k ₂ = (9.6 ± 1.0) × 10¹³ cm³mol⁻¹s⁻¹

  k ₃ = (8.0 ± 1.0) × 10¹³ cm³mol⁻¹s⁻¹

  k ₄ = (7.2 ± 0.8) × 10¹³ cm³mol⁻¹s⁻¹.

  The major products are the corresponding NH _i D_{2 − i} (X̃) radicals (i = 0, 1, 2), whereas quenching processes such as NH(a) + ND₃ → NH(X) + ND₃ are of minor importance (1%). The isotope exchange NH(a) + ND₃ → ND(X) + NHD₂ is negligible, and the corresponding channel on the singlet surface NH(a) + ND₃(X ^~) → ND(a) + NHD₂(X̃) contributes with 1% to the overall NH(a) depletion in that reaction. The experimental findings are discussed in terms of a chemical activation mechanism by means of statistical rate theory.

  摘要：在室温和10到20mbar的压力下，在He作为主要载气体的条件下，通过激光闪光光解HN3和DN3生成电子激发态反应物NH(a)和ND(a)，并通过激光诱导荧光(LIF)进行检测。同时，通过LIF检测到了NH(X)和ND(X)作为产物的基态物种。 通过伪一级条件下测量的NH(a)和ND(a)浓度-时间曲线，得到了以下速率常数： k1 = (9.1 ± 0.9) × 10^13 cm^3mol^-1s^-1 k2 = (9.6 ± 1.0) × 10^13 cm^3mol^-1s^-1 k3 = (8.0 ± 1.0) × 10^13 cm^3mol^-1s^-1 k4 = (7.2 ± 0.8) × 10^13 cm^3mol^-1s^-1. 主要产物是相应的NH_iD_2−_i(X̃)自由基(i = 0, 1, 2)，而NH(a) + ND3 → NH(X) + ND3等猝灭过程的重要性较小(1%)。同位素交换NH(a) + ND3 → ND(X) + NHD2可以忽略不计，而在单线态表面NH(a) + ND3(X̃) → ND(a) + NHD2(X̃)通道对整体NH(a)耗尽的贡献为1%。实验结果通过统计速率理论讨论了化学活化机制。
• Photodissociation dynamics of <i>A</i>̃ state ammonia molecules. II. The isotopic dependence for partially and fully deuterated isotopomers
  作者：David H. Mordaunt、Richard N. Dixon、Michael N. R. Ashfold

  DOI：10.1063/1.471368

  日期：1996.5

  The technique of H(D) Rydberg atom photofragment translational spectroscopy has been used to investigate the photodissociation dynamics of the mixed isotopomers NH2D and NHD2 following the excitation to the v2′=0 and 1 levels of their lowest lying Ã 1B1 (C2v) excited electronic states. Peaks in the resulting total kinetic energy release (TKER) spectra are assigned to levels of the NH2, NHD, or ND2 fragments with a wide range of quantum numbers Ka for rotation about their a inertial axes, and with N=Ka, N=Ka+1, or N=Ka+2 as appropriate. These data provide the first measurements of high rotational levels for the ground electronic state of the NHD radical. The least squares fitting of all these spectra, and those resulting from NH3 and ND3, to the best calculated NH2, NHD, and/or ND2 rotational term values provides accurate estimations of the respective N–H and N–D bond dissociation energies D00 across the whole series. These values are D00(H–NH2)=37 115±20 cm−1 (4.602±0.002 eV); D00(H–NHD)=37 240±50 cm−1; D00(H–ND2)=37 300±30 cm−1; D00(D–NHD)=37 880±60 cm−1; and D00(D–ND2)=38 010±20 cm−1. The differences between these values are fully consistent with differences in zero-point energies and lead to a mean value of De=40 510±25 cm−1. Dissociation of NH2D or NHD2 through their (Ã−X̃) 210 bands to give an NHD product leads to TKER spectra with a much higher statistical character than those leading to an NH2 or ND2 product, and to those obtained following excitation through the 000 bands. This is rationalized in a semiquantitative manner in terms of a varying contribution to the dissociation rate of the parent molecules from internal conversion (IC) to high levels of their respective ground states. Nuclear permutation symmetry appears to play an important role both for the IC rates and for the subsequent branching between product channels.
• Bond selectivity in the reaction of NH(<i>a</i> ¹Δ) with methanol
  作者：Satoru Okada、Atsumu Tezaki、Katsuyoshi Yamasaki、Hiroyuki Matsui

  DOI：10.1063/1.465086

  日期：1993.6

  Reaction of NH(a 1Δ) with methanol has been studied by a flash photolysis of HNCO at 193 nm at room temperature (298±2 K). Time dependence and relative concentrations for NH, NH2, NHD, CH3O, H, and D are monitored by a laser induced fluorescence (LIF) technique. From the pseudo-first-order analysis of NH(a 1Δ) decay rate, the rate constants for the reactions NH(a 1Δ)+CH3OH→ products (1), and NH(a 1Δ)+CH3OD→products (2) have been determined to be k1=(1.37±0.10)×10−10 cm3 molecule−1 s−1 in the pressure range of 3–20 Torr Ar or 5 Torr He, and k2=(1.33±0.05)×10−10 cm3 molecule−1 s−1 at the pressure of 5 Torr He, respectively. By comparing the LIF intensity of NH(X 3Σ−) in reaction (1) with that in NH(a 1Δ)+Xe reaction system, the contribution of physical quenching in reaction (1) has been evaluated to be less than 2.4%. Also by comparing the LIF intensities of NHD and NH2 in reaction (2) with those in NH(a 1Δ)+D2/H2 reaction systems, the branching ratio between the pathways producing NHD (2b) and NH2 (2c) has been determined to be k(2b)/k(2c)=23±9. It is elucidated that the insertion of NH(a 1Δ) into O–D bond of CH3OD is completely predominant over C–H bond; i.e., the O–D bond is about 69 times more reactive toward insertion of NH(a 1Δ) than a single C–H bond.
• Examination of the product channels in the reactions of NH(<i>a</i> ¹Δ) with H₂ and D₂
  作者：Atsumu Tezaki、Satoru Okada、Hiroyuki Matsui

  DOI：10.1063/1.464015

  日期：1993.3

  A flash photolysis study (193 nm) of HNCO has been conducted and the mechanisms of the reactions NH(a 1Δ)+H2→NH2+H(1) and NH(a 1Δ)+D2→products (2) have been examined in detail at 295±3 K by monitoring NH(a 1Δ), H, D, NH2, and their D substituents via the laser induced fluorescence technique. From the pseudo-first-order analysis of the decay rate for NH(a 1Δ), rate constants have been determined as k1=(3.96±0.17)×10−12 and k2=(2.62±0.08)×10−12. (All the rate constants are expressed in units of cm3 molecule−1 s−1.) These rate constants are consistent with those determined from the time dependence of H and D atoms: they are k1=(3.76±0.70)×10−12 and k2=(2.78±0.17)×10−12. No pressure dependence has been observed for 10–100 Torr He. The branching fraction for H and D atoms as products for reaction (2) has been found to be [H]/[D] =0.24/0.76, where D production is more abundant than statistically predicted. This indicates that reaction (2) is dominated by insertion of NH(a 1Δ) into the D2 bond, but vibrational energy of the reaction intermediate NHD2 is still localized in newly formed N–D bonds before it passes through the exit barrier into NHD+D or ND2+H channels. NH2(X̃ 2B1) was observed in (0,0,0) and (0,1,0) vibrational states as a product of reaction (1), and the observed time dependence of both vibrational states could be satisfactorily simulated by solving the master equation for vibrational relaxation of NH2. This analysis has indicated that the vibrational energy partitioning in the product NH2 is nearly statistical.
• The microwave spectrum of the NHD radical in the ground electronic state, 2A′′
  作者：Kaori Kobayashi、Hiroyuki Ozeki、Shuji Saito、Mizuho Tonooka、Satoshi Yamamoto

  DOI：10.1063/1.475224

  日期：1997.12.8

  The microwave spectrum of the monodeuterated species of NH2, NHD(X̃ 2A′′), was observed in the millimeter- and submillimeter-wave region. The NHD radical was produced by a dc-glow discharge through a NH3 and D2 mixture at around 220 K. Ten rotational transitions with both b- and a-type selection rules were observed in the 177–517 GHz region. The most important rotational transitions for astronomical observations, 101–000 and 110–101, were included and their detailed fine and hyperfine components were measured with high precision. The hyperfine interaction of the nitrogen, hydrogen, and deuterium nuclei, which are similar in magnitude, caused complicated hyperfine patterns and made their assignment relatively difficult. A least-squares analysis of the measured frequencies resulted in the determination of 40 molecular constants including nuclear spin–rotation coupling constants of N, H, D and, furthermore, nonaxial components of magnetic dipolar terms of H and D. The necessity of a higher K-dependent term of the dipole–dipole interaction constant for the hydrogen nucleus relative to the principal axis system reflects the effective geometrical change of the rotational levels.