chloro-trifluoro-[¹³C]methane | 70109-98-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 英文名称: chloro-trifluoro-[¹³C]methane
• 英文别名: freon-13；Trifluorchlormethan-<¹³C>
• CAS: 70109-98-7
• 化学式: CClF₃
• 分子量: 105.448
• InChiKey: AFYPFACVUDMOHA-OUBTZVSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.74
• 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：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  chloro-trifluoro-[¹³C]methane 、 钨 以 solid matrix 为溶剂， 生成
  参考文献：
  名称：

  Methylidyne XC⋮MX₃ (M = Cr, Mo, W; X = H, F, Cl) Diagnostic C−H and C−X Stretching Absorptions and Methylidene CH₂MX₂ Analogues

  摘要：

  Laser-ablated Cr, Mo, and W atoms react with di-, tri-, and tetrahalomethanes to form XC=MX3 (M Mo, W; X = H, F, Cl) methylidyne molecules as major products. Dihalomethanes also give a minor yield of CH2=MX2 methylidenes. The electronic state and bonding changes in the CH2=CrCl2, CH2=CrFCl, and CH2-CrF2 methylidene series, but the Mo and W counterparts are calculated to be triplet state CH2=MX2 molecules. Identifications of these new carbon-metal multiple bond species are made through isotopic substitution (D, C-13) and isotopic frequency calculations using density functional theory. The HC=MX3 molecules exhibit C-H stretching frequencies in the 3030-3090 cm(-1) region and C=M stretching frequencies in the 1007-980 cm(-1) range, which vary slightly with the carbon hybridization as determined by the substituents employed here. The XC=MX3 molecules show very high C-X stretching frequencies in the 1540-1520 cm(-1) region for X = F and 1300-1230 cm(-1) for X = Cl due to strong bonds and the antisymmetric nature of the X-C-M vibrational mode.

  DOI：

  10.1021/om700689e

文献信息

• 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。
• Reactions of Laser-Ablated Iron Atoms with Halomethanes: Infrared Spectra, Density Functional Calculations, and Structures of Simple Iron Insertion and Methylidene Complexes
  作者：Han-Gook Cho、Jonathan T. Lyon、Lester Andrews

  DOI：10.1021/om8005189

  日期：2008.10.27

  Only insertion complexes are identified from reactions of Fe with methyl fluoride and ethane, parallel to the previously observed insertion complex CH3−FeH from the photochemical reaction with methane. However, Fe also forms methylidene complexes through α-X migration in the insertion products from Fe reactions with di-, tri-, and tetrahalomethanes. Calculated structures show no agostic distortion in

  通过基体红外光谱和密度泛函计算，研究了激光烧蚀的Fe原子与卤代甲烷和乙烷的反应。从Fe与甲基氟和乙烷的反应中只能识别出插入配合物，这与之前从甲烷与光化学反应中观察到的插入配合物CH 3 -FeH平行。然而，铁还通过铁与二卤代，三卤代和四卤代甲烷反应的插入产物中的α-X迁移而形成亚甲基络合物。计算的结构表明在这些亚甲基络合物中没有任何扭曲。然而，在Fe插入产物（例如H 2）中观察到了有趣的C-Cl键变形和伸长ClC-FeCl，而在H 2 FC-FeCl的类似计算结构中未发现CH或CF键的这种变形。这种畸变可能是由于为C1孤对与Fe结合相互作用，最终导致形成较低能量的CH 2 ═FeCl 2亚甲基络合物。这种Cl原子的转移在可见紫外线照射下是可逆的。没有证据表明最近在Ru中观察到这种类型的亚甲基二炔配合物，因为这种较高的氧化态结构在家族中越稳定。
• Group 4 Metal Atom Reactions with CF₃Cl, CFCl₃, CF₃Br, and CF₃I:  A Matrix Infrared Spectroscopic and DFT Investigation of Competitive α-Halogen Transfer to Form Triplet XC÷MX₃ Complexes
  作者：Jonathan T. Lyon、Lester Andrews

  DOI：10.1021/om0702025

  日期：2007.8.1

  Laser-ablated group 4 transition metal atoms react with CX1X23 (X = F, Cl, Br, or I) to form triplet state X1C÷MX23 and X2C÷MX1X22 complexes, which are identified by their infrared spectra, carbon-13 isotopic shifts, and comparison to density functional vibrational frequency calculations. The higher energy product with more heavier halogen migration converts to the lower energy product with more α-F

  激光烧蚀的第4组过渡金属原子与CX 1 X 2 3（X = F，Cl，Br或I）反应形成三重态X 1 C÷MX 2 3和X 2 C÷MX 1 X 2 2配合物，通过红外光谱，碳13同位素位移以及与密度函数振动频率计算的比较来识别。卤素迁移更重的高能积转化为紫外线照射下具有更多α-F转移的低能积。这些产物配合物中特别有两个特征：第一个特征是存在非常强的C-X键，第二个特征是碳上两个不成对的电子与过渡金属中心共享，从而形成缺电子的三重态键。对与CF 4，CCl 4和CF 2 Cl 2的类似反应产物进行了比较。
• Infrared and DFT Investigations of the XC⋮ReX₃ and HC⋮ReX₃ Complexes:  Jahn−Teller Distortion and the Methylidyne C−X(H) Stretching Absorptions
  作者：Jonathan T. Lyon、Han-Gook Cho、Lester Andrews、Han-Shi Hu、Jun Li

  DOI：10.1021/ic701014u

  日期：2007.10.1

  The XC ReX3 complexes (X = F, Cl) are produced by CX4 reaction with laser-ablated Re atoms, following oxidative C-X insertion and alpha-halogen migration in favor of the carbon-metal triple bond and are identified through the observation of characteristic absorptions in the argon matrix infrared spectra and comparison with vibrational frequencies calculated by density functional theory. The methylidyne C-F and C-Cl stretching absorptions are observed near 1584 and 1328 cm(-1), and the C-H stretching modes for HC ReX3 at 3104 and 3097 cm(-1), respectively, which are substantially higher than the precursor stretching modes and in agreement with the general trend that higher s-orbital character in carbon hybridization leads to a higher stretching frequency. The Jahn-Teller effect in the doublet-state XC ReX3 and HC ReX3 complexes gives rise to distorted structures with C-S symmetry and two equivalent longer Re-X bonds and one slightly shorter Re-X bond.