1-diazo-2,4-pentadiyne | 882044-91-9

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 炔丙基型1，3-偶极有机化合物
• 英文名称: 1-diazo-2,4-pentadiyne
• 英文别名: 5-Diazopenta-1,3-diyne；5-diazopenta-1,3-diyne
• CAS: 882044-91-9
• 化学式: C₅H₂N₂
• 分子量: 90.0843
• InChiKey: ACUXIVZBHPUSPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-diazo-2,4-pentadiyne 生成 pentadiynylidene
  参考文献：
  名称：

  五角叉亚萘基及其甲基取代的衍生物：R 1 -C 5 -R 2三重碳链的阈值光电子能谱

  摘要：

  气相中的质量选择阈值光电子能谱用于表征二炔基三重态碳戊二烯戊二炔（HC 5 H），甲基戊二炔（MeC 5 H）和二甲基戊二炔（MeC 5 Me）。重氮化合物被用作前体通过闪速热解生成羧甲基。在光电子光子重合（PEPICO）实验中，通过真空紫外（VUV）同步辐射将R 1 -C 5 -R 2碳链光电离。进行了从头算起的高级计算，以支持对实验的解释。对于未取代的戊二炔（R 1 = R 2= H）记录的光谱产生的绝热电离能（IE ad）为8.36±0.03 eV。此外，根据8.60±0.03 eV的IE ad和Franck-Condon模拟，在光谱中鉴定出第二个卡宾异构体3-（二氢亚乙烯基）环丙烯，具有单重电子基态。我们发现需要多参考计算才能可靠地计算该分子的IE广告。CASPT2计算可预测IE广告= 8.55 eV，而耦合群集计算大大高估了IE。环状异构体很可能由样品中存在的前体的另一种异构体形

  DOI：

  10.1021/acs.jpca.8b12244
• 作为产物：
  描述：

  (Z)-1-chloro-5,5-diethoxy-1-penten-3-yne 在 硫酸 、 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 23.0h， 生成 1-diazo-2,4-pentadiyne
  参考文献：
  名称：

  Reactive Carbon-Chain Molecules:  Synthesis of 1-Diazo-2,4-pentadiyne and Spectroscopic Characterization of Triplet Pentadiynylidene (H−C⋮C−C̈−C⋮C−H)

  摘要：

  1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers; 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N-2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C equivalent to C-C-C equivalent to C-H). Theory predicts an axially symmetric (D-h) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (vertical bar D/hc vertical bar = 0.6157 cm(-1), vertical bar E/hc vertical bar = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O-2-cloped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

  DOI：

  10.1021/ja058252t

文献信息

• Reactive Carbon-Chain Molecules:  Synthesis of 1-Diazo-2,4-pentadiyne and Spectroscopic Characterization of Triplet Pentadiynylidene (H−C⋮C−C̈−C⋮C−H)
  作者：Nathan P. Bowling、Robert J. Halter、Jonathan A. Hodges、Randal A. Seburg、Phillip S. Thomas、Christopher S. Simmons、John F. Stanton、Robert J. McMahon

  DOI：10.1021/ja058252t

  日期：2006.3.1

  1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers; 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N-2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C equivalent to C-C-C equivalent to C-H). Theory predicts an axially symmetric (D-h) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (vertical bar D/hc vertical bar = 0.6157 cm(-1), vertical bar E/hc vertical bar = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O-2-cloped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.
• Pentadiynylidene and Its Methyl-Substituted Derivates: Threshold Photoelectron Spectroscopy of R₁-C₅-R₂ Triplet Carbon Chains
  作者：Engelbert Reusch、Dustin Kaiser、Domenik Schleier、Rachel Buschmann、Anke Krueger、Thomas Hermann、Bernd Engels、Ingo Fischer、Patrick Hemberger

  DOI：10.1021/acs.jpca.8b12244

  日期：2019.3.14

  the experiments. For the unsubstituted pentadiynylidene (R1 = R2 = H) the recorded spectrum yields an adiabatic ionization energy (IEad) of 8.36 ± 0.03 eV. In addition, a second carbene isomer, 3-(didehydrovinylidene)cyclopropene, with a singlet electronic ground state, was identified in the spectrum based on the IEad of 8.60 ± 0.03 eV and Franck–Condon simulations. We found that multireference computations

  气相中的质量选择阈值光电子能谱用于表征二炔基三重态碳戊二烯戊二炔（HC 5 H），甲基戊二炔（MeC 5 H）和二甲基戊二炔（MeC 5 Me）。重氮化合物被用作前体通过闪速热解生成羧甲基。在光电子光子重合（PEPICO）实验中，通过真空紫外（VUV）同步辐射将R 1 -C 5 -R 2碳链光电离。进行了从头算起的高级计算，以支持对实验的解释。对于未取代的戊二炔（R 1 = R 2= H）记录的光谱产生的绝热电离能（IE ad）为8.36±0.03 eV。此外，根据8.60±0.03 eV的IE ad和Franck-Condon模拟，在光谱中鉴定出第二个卡宾异构体3-（二氢亚乙烯基）环丙烯，具有单重电子基态。我们发现需要多参考计算才能可靠地计算该分子的IE广告。CASPT2计算可预测IE广告= 8.55 eV，而耦合群集计算大大高估了IE。环状异构体很可能由样品中存在的前体的另一种异构体形