methylidynephosphine | 6829-52-3

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: methylidynephosphine
• 英文别名: phosphaethyne；Methinophosphide；methylidynephosphane
• CAS: 6829-52-3
• 化学式: CHP
• 分子量: 43.9927
• InChiKey: DPYPSJGRRFKXBE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  2
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  苯甲腈 N-氧化物 、 methylidynephosphine 以 乙醚 为溶剂， 以9%的产率得到2,8-diphenyl-3,7-diaza-4,6-dioxa-1-phosphabicyclo<3.3.0>octa-2,7-dien
  参考文献：
  名称：

  Ungewöhnlich koordinierte Phosphorverbindungen

  摘要：

  DOI：

  10.1016/0022-328x(88)80006-8
• 作为产物：
  描述：

  dichloromethylphosphine 在 potassium carbonate 作用下， 生成 methylidynephosphine
  参考文献：
  名称：

  The Gas-Phase Acidity of HCP, CH3CP, HCAs, and CH3CAs: An Unexpected Enhanced Acidity of the Methyl Group

  摘要：

  The gas-phase acidities of methylidynephosphine, HC=P. ethylidynephosphine. CH3C=P. and ethylidynearsine, CH3C=As, have been measured by means of Fourier Transform Ion Cyclotron Resonance (FTICR) mass spectrometry and calculated Lit the CCSD(T)/6-311+G(3df,2p)//QCISD/ 6-311 + G(df.p) level of theory. An analysis of these results shows that, in contrast to the well-known fact that HC=N is a stronger acid than CH3C=N, CH3C=P and CH3C=As are more acidic than HC=P and HC=As, respectively. The most important consequence of this unexpected effect is that while HC=P and HC=As are found to be weaker acids than HC=N. the opposite trend is found for the corresponding methyl derivatives, the acidity of which increases as CH3C=N < CH3C=P < CH3C=As. Also the effects of deprotonation on the structures and the vibrational frequencies of HC=X and CH3C=X (X=N, P, As) compounds are qualitatively similar. but quantitatively very different for nitrogen- as compared with phosphorus- and arsenic-containing compounds. A rationalization of these differences in terms of the bonding differences is presented.

  DOI：

  10.1002/1521-3765(20021104)8:21<4919::aid-chem4919>3.0.co;2-j

文献信息

• The detection of some new phosphaalkynes, RCP, using microwave spectroscopy
  作者：J.C.T.R.Burckett St. Laurent、T.A. Cooper、H.W. Kroto、J.F. Nixon、O. Ohashi、K. Ohno

  DOI：10.1016/0022-2860(82)85054-0

  日期：1982.1

  Using flow-pyrolysis techniques together with microwave and other spectroscopic detection methods it has proven possible to produce and study new substituted analogues of phosphaethyne. HCP. The intial work on CH3CP, FCP and CF3CP as well as HCP itself has now been extended to the production and study of NC-CP, HCC-CP, CH2CHCP and PhCP.

  使用流动热解技术以及微波和其他光谱检测方法，已证明可以生产和研究新的磷炔类似物。HCP. CH3CP、FCP和CF3CP以及HCP本身的初步工作现已扩展到NCCP、HCCCP、CH2CHCP和博士P.
• High resolution FT-IR spectra of the ν1, ν2, and ν3 bands of H12CP and of the ν1 and ν2 bands of H13CP
  作者：Michael Jung、Brenda P. Winnewisser、Manfred Winnewisser

  DOI：10.1016/s0022-2860(96)09751-7

  日期：1997.9

  were assigned and analysed. In the second region, the fundamental band ν3, its hot band from v2 = 1, and the overtone of ν2 and its hot bands could be measured, and in the third region. ν1 and its hot bands. The fundamental and overtone bands of the bending vibration of H13CP, and its hotbands from v2 = 1 and 2, as well as the ν1 fundamental were also assigned and analysed. The bands observed for

  摘要 通过 CH3PCl2（二氯甲基膦）的热解合成了 HCP（膦乙炔）样品。H13CP 以自然丰度存在。高分辨率光谱是使用 BRUKER IFS 120 HR 傅立叶变换光谱仪测量的，使用 3 米吸收池，以及吸收路径长度高达 19.68 米的怀特型池。测量的波数区域分别为 400-725、1200-1850 和 2500-3600 cm-1，分辨率分别为 0.0018、0.0024 和 0.0048 cm-1。在最低波数区，ν2 基带，来自 v2 = 1,2,3 和 v3 = 1 的热带，以及一个费米共振诱导带，( v 1 vl 2 2 v 3 ) = (00 Oc 1) « (01 le 0 )，被分配和分析。在第二个区域中，可以测量基带 ν3 及其来自 v2 = 1 的热带，以及 ν2 的泛音及其热带，在第三个区域中。ν1 及其热带。还分配和分析了 H13CP 弯曲振动的基波和泛音带，以及
• A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion
  作者：Wesley J. Transue、Alexandra Velian、Matthew Nava、Marie-Aline Martin-Drumel、Caroline C. Womack、Jun Jiang、Gao-Lei Hou、Xue-Bin Wang、Michael C. McCarthy、Robert W. Field、Christopher C. Cummins

  DOI：10.1021/jacs.6b03910

  日期：2016.6.1

  Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported here as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been observed by molecular beam mass spectrometry, laser-induced fluorescence, microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation

  Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) 在此被报道为磷炔 (HC≡P) 的分子前体，与蒽和三苯基膦一起生产。已通过分子束质谱、激光诱导荧光、微波光谱和核磁共振 (NMR) 光谱观察到由 1 热解产生的 HCP。在甲苯中，已发现 1 的裂解以 ΔH(⧧) = 25.5 kcal/mol 和 ΔS(⧧) = -2.43 eu 的活化参数进行，并伴随形成橙色不溶性沉淀。HCP 生成机制的计算研究结果与实验数据非常一致。这种高温生成 HCP 的方法指出了与叠氮化物阴离子的新反应化学，以产生 1,2,3,4-磷酸三唑根阴离子，HCPN3(-)，其结构数据已在单晶 X 射线衍射研究中获得。负离子光电子能谱显示该阴离子的绝热脱离能量为 3.555(10) eV。HCPN3(-) 的芳香性已使用与核无关的化
• Detection of C-cyanophosphaethyne, NC–CP, by microwave spectroscopy
  作者：Terry A. Cooper、Harold W. Kroto、John F. Nixon、Osamu Ohashi

  DOI：10.1039/c39800000333

  日期：——

  The microwave spectrum of the new species C-cyanophosphaethyne NC–CP has been detected in the products of a gas phase high temperature (ca. 700 °C) reaction between cyanogen azide, NCN3, and phosphaethyne, HCP; the new species which is the monophosphorus analogue of cyanogen, (CN)2, has a dipole moment of 3·5 D.

  在叠氮化氰NCN 3和磷乙炔HC P之间的气相高温（约700°C）反应产物中检测到了新物种C-氰基磷乙炔N C–C P的微波光谱；该新物种是氰（CN）2的单磷类似物，其偶极矩为3·5D。
• Lamb-dip millimeter-wave spectroscopy of HCP: Experimental and theoretical determination of 31P nuclear spin–rotation coupling constant and magnetic shielding
  作者：L. Bizzocchi、C. Degli Esposti、L. Dore、C. Puzzarini

  DOI：10.1016/j.cplett.2005.03.134

  日期：2005.6

  have been recorded with sub-Doppler resolution using the Lamb-dip technique. The hyperfine structure due to the magnetic coupling between rotation and phosphorus nuclear spin has been resolved, yielding the value of the phosphorus spin–rotation constant, C(P) = 43.64 ± 0.15 kHz, from which the corresponding absolute magnetic shielding has been derived: σ(P) = 373 ± 2 ppm. Theoretical values of C(P) and

  半稳定的HCP分子是通过膦和氯仿的气相二氢裂解制得的。 使用Lamb-dip技术以亚多普勒分辨率记录了三个旋转跃迁J = 2←1、3←2和4←3。旋转和磷核自旋之间的磁耦合导致的超精细结构已得到解决，得出了磷自旋-旋转常数C（P）= 43.64±0.15 kHz的值，由此得出了相应的绝对磁屏蔽：σ（P）= 373±2 ppm。还已在CCSD（T）的理论水平上计算了HCP和NP的C（P）和σ（P）的理论值。