二氟甲烷-D2 | 594-24-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 中文名称: 二氟甲烷-D2
• 中文别名: 二氟甲烷-d2
• 英文名称: difluoromethane-d2
• 英文别名: Methylenfluorid-d2；Difluoromethane-d2；dideuterio(difluoro)methane
• CAS: 594-24-1
• 化学式: CH₂F₂
• 分子量: 54.0078
• InChiKey: RWRIWBAIICGTTQ-DICFDUPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二氟甲烷-D2 在 氯 作用下， 生成 CDF2Cl
  参考文献：
  名称：

  Time lags and V-V' steady states in the infrared laser induced decomposition of chlorodifluoromethane and chlorodifluoromethane-d1 under collisional conditions

  摘要：

  DOI：

  10.1021/ja00375a013
• 作为产物：
  描述：

  三氟碘甲烷 在 Ni⁽¹¹¹⁾, D 作用下， 生成 四氟乙烯 、 四氟化碳 、 二氟甲烷 、 二氟甲烷-D2 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Adsorption and Reaction of Trifluoromethyl Iodide on Ni(111)

  摘要：

  We have investigated the surface chemistry of trifluoromethyl iodide adsorbed on Ni(111) under ultrahigh-vacuum conditions using temperature-programmed desorption, reflection absorption infrared spectroscopy, and Auger electron spectroscopy. Ni(111) activates both carbon-iodine and carbon-fluorine bonds in adsorbed CF3I. Atomic iodine desorbs from the surface near 975 K, and nickel fluoride, NiF2, desorbs near 820 K. Although the desorption temperatures for iodine and nickel fluoride are high, there is evidence that carbon-iodine and carbon-fluorine bonds are activated below room temperature. A small amount of fluorocarbon products containing CF2 and CF3 fragments desorb from the surface between 200 and 375 K. At higher temperatures, fluorine atoms recombine with adsorbed carbon to form CF4, which desorbs near 780 K. CF3I molecularly desorbs from the surface at high coverages with desorption rate maxima of 162 and 122 K for the monolayer and multilayer, respectively. Coadsorption of D atoms and CF3I results in the desorption of CD2F2 near 230 K and DF between 260 and 460 K. After desorption of the monolayer, the bands in the infrared spectrum are quite weak. The IR data suggest that very few fluorocarbon fragments are stabilized on the surface. In general, the data indicate that a large fraction of adsorbed CF3I decomposes to form atomic carbon, fluorine and iodine. A comparison of the reactions of CF3I on Ni to Ag, Pt and Ru shows that only Ni is etched under ultrahigh-vacuum conditions by CF3I.

  DOI：

  10.1021/j100015a048

文献信息

• Infrared Spectra and Electronic Structures of Agostic Uranium Methylidene Molecules
  作者：Jonathan T. Lyon、Lester Andrews、Han-Shi Hu、Jun Li

  DOI：10.1021/ic701786h

  日期：2008.3.1

  Through reactions of laser-ablated uranium atoms with methylene halides CH2XY (XY = F2, FCl, and Cl2), a series of new actinide methylidene molecules CH2UF2, CH2UFCl, and CH2UCl2 are formed as the major products. The identification of these complexes has been accomplished via matrix infrared spectra, isotopic substitution, and relativistic density functional calculations of the vibrational frequencies

  通过激光烧蚀的铀原子与卤化甲烷CH2XY（XY = F2，FC1和Cl2）的反应，形成了一系列新的act系亚甲基分子CH2UF2，CH2UFCl和CH2UCl2。这些配合物的鉴定已通过矩阵红外光谱，同位素取代以及振动频率和红外强度的相对论密度泛函计算完成。使用广义梯度法（PW91）进行的密度泛函计算表明，这些CH2UXY亚甲基络合物更倾向于高度扭曲的无序结构，而不是像乙烯一样的对称结构。对于所有三个铀配合物，计算出的偏航角（θHCU）约为89度，并且预测的振动模式和同位素位移与实验值非常吻合。电子结构计算表明，这些U（IV）分子在具有5f（2）构型的三重态基态中均具有很强的C = U双键。计算出的键长和键能表明，由于氟取代基的诱导作用，U（6d）轨道的径向收缩，氟化物中的C = U双键比氯化物中的弱。比较了该铀铀亚甲基配合物与类似的过渡金属和or配合物，发现它们在化学上存在有趣的差异。计算
• Infrared Spectra of CX₃−MnX and CX₂═MnX₂(X = H, F, Cl) Prepared in Reactions of Laser-Ablated Manganese Atoms with Halomethanes
  作者：Han-Gook Cho、Lester Andrews

  DOI：10.1021/om100791h

  日期：2011.2.14

  calculations. The Mn methylidenes have planar structures, common among early transition-metal analogues, revealing that Mn has borderline properties between the early and late transition metals. The computed C−Mn bond lengths of the carbene complexes in the quartet states (1.855−1.872 Å) are considerably shorter than those of the insertion complexes in the sextet states (2.057−2.120 Å), which is likely due to

  小锰插入（CX 3 -MnX）和亚甲基（CX 2 ═MnX 2）配合物在激光烧成的Mn原子与卤代甲烷的反应中产生，在类似的3-12组金属配合物中具有最高的多重性（六重态和四重态），并通过同位素位移和DFT频率计算在基体红外光谱中鉴定出来。Mn插入配合物的线性C-M-X结构类似于格氏试剂分子，不同于除Fe以外的其他过渡金属类似物，并且根据DFT计算，Mn-C键具有高s特性。Mn亚甲基具有早期过渡金属类似物中常见的平面结构，这表明Mn在早期过渡金属和晚期过渡金属之间具有边界性质。卡宾配合物在四重态下的计算出的C-Mn键长（1.855-1。（872Å）比六重态下的插入配合物（2.057−2.120Å）短得多，这很可能是由于半键π键阶和离子对卡宾配合物中键合的贡献很大。在第7族金属Mn和Re中，随着族群的下降，对较高氧化态产物的偏好增加的趋势最为明显。
• Formation of carbyne complexes in reactions of laser-ablated Os atoms with halomethanes: characterization by C–H(X) and Os–H(X) stretching absorptions and computed structures
  作者：Han-Gook Cho、Lester Andrews

  DOI：10.1039/b811805a

  日期：——

  Reactions of laser-ablated Os atoms with halomethanes have been investigated. Small carbyne complexes are produced in reactions of Os atoms with fluoromethanes and identified through matrix infrared spectra and vibrational frequencies computed by density functional theory. The preference for the carbon–osmium triple bond is traced to the low energy of the Os carbyne products. The C–H and C–X stretching absorptions of the carbyne complexes are observed on the high frequency sides of the corresponding precursor bands, which result from the high s character in the C–H bond and interaction between the C–X and C–Os stretching modes, respectively. The calculated Os complex structures show a large variation with the ligands and electronic states, similar to the analogous Ru complex structures. The present report also compares previous Fe, Ru, and Os results and supports the general trend that the higher oxidation state complexes become more stable on going down the family group column.

  激光烧蚀的铼（Os）原子与卤甲烷的反应已被研究。在Os原子与氟甲烷的反应中产生了小的炭烯复合物，并通过矩阵红外光谱和密度泛涵理论计算的振动频率进行了识别。碳-铼三键的偏好归因于Os炭烯产物的低能量。炭烯复合物的C-H和C-X拉伸吸收位于相应前驱体带的高频侧，这分别是由于C-H键中高的s特性以及C-X和C-Os拉伸模式之间的相互作用。计算得到的Os复合物结构随着配体和电子状态的变化而变化很大，类似于类比的铑（Ru）复合物结构。本报告还比较了之前的铁（Fe）、铑（Ru）和铼（Os）结果，并支持了一个一般趋势，即随着族列的下降，更高氧化态的复合物变得更加稳定。
• Infrared spectra of XCIrX3 and CX2IrX2 prepared by reactions of laser-ablated iridium atoms with halomethanes
  作者：Han-Gook Cho、Lester Andrews

  DOI：10.1039/c002347g

  日期：——

  oxidation-state complexes with carbon–iridium multiple bonds are identified in the product matrix infrared spectra from reactions of laser-ablated Ir atoms with tetra-, tri- and dihalomethanes. In contrast to the previously studied Rh case, Ir carbyne complexes (XCIrX3) are generated in reactions of tetrahalomethanes, and their short Ir–C bond lengths of 1.725–1.736 Å are appropriate for the carbon–metal triple

  小的 铱 高氧化态配合物 碳–铱 通过激光烧蚀的反应在产物矩阵红外光谱中鉴定出多个键 铱含四，三和二卤甲烷的原子。与之前研究的相反铑 案子， 卡宾配合物（XC IrX 3）是在四卤甲烷的反应中生成的，其Ir-C键较短的1.725-1.736Å长适合碳-金属三键。DFT计算还表明，具有Ir–F键的Ir卡宾烯具有不寻常的正方形平面结构，类似于最近发现的茹平面络合物。对卡宾 络合物导致三叉和双叉中的亚甲基产物吸收 二卤甲烷光谱，标志着生成小金属卡宾的极限。另一方面，在本研究中未观察到插入复合物，表明X从C 到 铱 初始C–X插入后很快。
• Reactions of Thorium Atoms with Polyhalomethanes: Infrared Spectra of the CH ₂ =ThX ₂ , HC÷ThX ₃ , and XC÷ThX ₃ Molecules
  作者：Jonathan T. Lyon、Lester Andrews

  DOI：10.1002/ejic.200701048

  日期：2008.3

  and density functional theoretical calculations confirm the identity of these methylidene and methylidyne complexes. Parallels with the analogous chloromethane and Group 4 metal reaction products are discussed. Structure calculations show that the C=Th bond lengths decrease and the agostic distortion increases from CH2=ThF2 to CH2=ThFCl to CH2=ThCl2 for the methylidene complexes. The triplet-state HC÷ThF3

  激光烧蚀的钍原子与亚甲基氟化物反应形成单线态 CH2=ThF2，与氟形成三线态 HC÷ThF3，与 CF4 产生三线态 FC÷ThF3 分子作为固体氩气中的主要产物。红外光谱、同位素取代和密度泛函理论计算证实了这些亚甲基和亚甲基配合物的身份。讨论了与类似的氯甲烷和第 4 族金属反应产物的相似之处。结构计算表明，对于亚甲基配合物，C=Th 键长减少，前向畸变从 =ThF2 到 =ThFCl 再到 =ThCl2。三重态 HC÷ThF3 和 FC÷ThF3 缺电子甲基化炔配合物表现出离域键合，这由与类似锆配合物计算的自旋密度相当的自旋密度证明。氯取代氟支持更强的 C÷Th 键。因此，钍似乎作为早期的过渡金属原子与氟甲烷和氯甲烷反应。然而，除了 SOMO 中的 6d 之外，Th 5f 轨道也有很大的贡献，在这些缺电子的甲基炔配合物中形成弱 π 键。（© Wiley-VCH Verlag