diphenylacetylene-1-13C-d5 | 828919-49-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diphenylacetylene-1-13C-d5
• 英文别名: diphenylacetylene-d10,13C；C6D5C(13)CC6D5
• CAS: 828919-49-9
• 化学式: C₁₄H₁₀
• 分子量: 189.143
• InChiKey: JRXXLCKWQFKACW-LLJFSLRSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.09
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  氢气 、 diphenylacetylene-1-13C-d5 、 [Pt((t)bucope)(OTf)2] 以 CD₂Cl₂ 为溶剂， 生成 [Pt((t)bucope)((13)CHC6D5(13)CH2C6D5)](OTf)
  参考文献：
  名称：

  A parahydrogen based NMR study of Pt catalysed alkyne hydrogenation

  摘要：

  基于顺磁氢的核磁共振研究揭示了在甲醇中，铂(II)双膦三氟甲磺酸盐催化炔烃氢化反应中，铂双膦烷基正离子和甲醇功能化的铂双膦烷醚正离子是观察到的烯烃和乙烯基醚产物的责任中心。

  DOI：

  10.1039/b925196k
• 作为产物：
  描述：

  在 tris(dibenzylideneacetone)dipalladium (0) 、 palladium diacetate 三叔丁基膦 、 五氯化磷 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 乙醚 、 苯 为溶剂， 反应 13.0h， 生成 diphenylacetylene-1-13C-d5
  参考文献：
  名称：

  A para-Hydrogen Investigation of Palladium-Catalyzed Alkyne Hydrogenation

  摘要：

  The complexes [Pd(bcope)(OTf)(2)] (1a), where bcope is (C8H14)PCH2-CH2P(C8H14), and [Pd((t)bucope)(OTf)(2)] (1b), where (t)bucope is (C8H14)PC6H4CH2P(Bu-t)(2), catalyze the conversion of diphenylacetylene to cis- and trans-stilbene and 1,2-diphenylethane. When this reaction was studied with para-hydrogen, the characterization of [Pd(bcope)(CHPhCH2Ph)](OTf) (2a) and [Pd((t)bucope)(CHPhCH2Ph)](OTf) (2b) was achieved. Magnetization transfer from the alpha-H of the CHPhCH2Ph ligands in these species proceeds into trans-stilbene. This process has a rate constant of 0.53 s(-1) at 300 K in methanol-d(4) for 2a, where Delta H-double dagger = 42 +/- 9 kJ mol(-1) and Delta S-double dagger = -107 +/- 31 J mol(-1) K-1, but in CD2Cl2 the corresponding rate constant is 0.18 s(-1), with Delta H-double dagger = 79 +/- 7 kJ mol(-1) and Delta S = 5 +/- 24 J mol(-1) K-1. The analogous process for 2b was too fast to monitor in methanol, but in CD2Cl2 the rate constant for trans-stilbene formation is 1.04 s(-1) at 300 K, with Delta H = 94 +/- 6 kJ mol(-1) and Delta S = 69 +/- 22 J mol(-1) K-1. Magnetization transfer from one of the two inequivalent beta-H sites of the CHPhCH2Ph moiety proceeds into trans-stilbene, while the other site shows transfer into H-2 or, to a lesser extent, cis-stilbene in CD2Cl2, but in methanol it proceeds into the vinyl cations [Pd(bcope)(CPhCHPh)(MeOD)](OTf) (3a) and [Pd((t)bucope)(CPhCHPh)(MeOD)](OTf) (3b). When the same magnetization transfer processes are monitored for 1a in methanol-d(4) containing 5 mu L of pyridine, transfer into trans-stilbene is observed for two sites of the alkyl, but the third proton now becomes a hydride ligand in [Pd(bcope)(H)(pyridine)](OTf) (5a) or a vinyl proton in [Pd(bcope)(CPhCHPh)(pyridine)](OTf) (4a). For 1b, under the same conditions, two isomers of [Pd((t)bucope)(H)(pyridine)](OTf) (5b and 5b') and the neutral dihydride [Pd((t)bucope)(H)(2)] (7) are detected. The single vinylic CH proton in 3 and the hydride ligands in 4 and 5 appear as strong emission signals in the corresponding H-1 NMR spectra.

  DOI：

  10.1021/ja070331c

文献信息

• An NMR study of cobalt-catalyzed hydroformylation using para-hydrogen induced polarisation
  作者：Cyril Godard、Simon B. Duckett、Stacey Polas、Robert Tooze、Adrian C. Whitwood

  DOI：10.1039/b815853c

  日期：——

  The syntheses of Co(eta3-C3H5)(CO)2PR2R' (R, R' = Ph, Me; R, R' = Me, Ph; R = R' = Ph, Cy, CH2Ph) and Co(eta3-C3H5)(CO)(L) (L = dmpe and dppe) are described, and X-ray structures for Co(eta3-C3H5)(CO)(dppe) and the PPh2Me, PCy3 derivatives reported. The relative ability of Co(eta3-C3H5)(CO)2(PR2R') to exchange phosphine for CO follows the trend PMe2Ph < PPh2Me < PCy3 < P(CH2Ph)3 < PPh3. Reactions of the

  Co（eta3-C3H5）（CO）2PR2R'（R，R'= Ph，Me; R，R'= Me，Ph; R = R'= Ph，Cy，CH2Ph）和Co（eta3- ）（CO）（L）（L = dmpe和dppe）进行了描述，并报道了Co（eta3- ）（CO）（dppe）和PPh2Me，PCy3衍生物的X射线结构。Co（eta3- ）（CO）2（PR2R'）的膦转化为CO的相对能力遵循PMe2Ph
• Palladium catalysed alkyne hydrogenation and oligomerisation: a parahydrogen based NMR investigation
  作者：Joaquín López-Serrano、Simon B. Duckett、John P. Dunne、Cyril Godard、Adrian C. Whitwood

  DOI：10.1039/b804162h

  日期：——

  The role phosphine ligands play in the palladium(II)-bis-phosphine-hydride cation catalysed hydrogenation of diphenylacetylene is explored through a PHIP (parahydrogen induced polarization) NMR study. The precursors Pd(LL′)(OTf)2 (1a–e) [LL′ = dcpe (PCy2CH2CH2PCy2), dppe, dppm, dppp, cppe (PCy2CH2CH2PPh2)] are used. Alkyl palladium intermediates of the type [Pd(LL′)(CHPhCH2Ph)](OTf) (2 and 3) are detected and demonstrated to play an active role in hydrogenation catalysis. Magnetization transfer experiments reveal chemical exchange from the α-H of the alkyl ligand of 2a (LL′ = dcpe) and linkage isomer 2e′ (LL′ = cppe) into trans-stilbene on the NMR timescale. Activation parameters (ΔH≠ and ΔS≠) for this transformation have been determined. These experiments, coupled with GC/MS data, indicate that the catalytic activity is greater in methanol, where it follows the order: dcpe > cppe > dppp > dppe > dppm, than in CD2Cl2. All five of the phosphine systems described are less active than those based on bcope [where bcope is (C8H14)PCH2–CH2P(C8H14)] and tbucope [where tbucope is (C8H14)PC6H4CH2P(tBu)2]. cis, cis-1,2,3,4-Tetraphenyl-buta-1,3-diene is detected as a minor reaction product with Pd(LL′)(PhCH–CHPh–CPhCHPh)+ (4) also being shown to play a role in the alkyne dimerisation step.

  通过PHIP（对氢诱导极化）NMR研究探讨了膦配体在钯(II)-双膦-氢阳离子催化苯基乙炔氢化反应中的作用。使用的前体为Pd(LL′)(OTf)₂（1a-e）[LL′ = dCPe（PCy₂CH₂CH₂PCy₂），dppe，dppm，dppp，CPpe（PCy₂CH₂CH₂PPh₂）]。检测到类型为[Pd(LL′)(CHPhCH2Ph)](OTf)（2和3）的烷基钯中间体，并证明其在氢化催化中发挥了积极作用。磁化转移实验揭示了来自2a（LL′ = dCPe）和连接异构体2e′（LL′ = CPpe）烷基配体的α-H在NMR时间尺度上与反式stilbene之间的化学交换。已确定该转化的活化参数（ΔH≠和ΔS≠）。这些实验结合GC/MS数据表明，在甲醇中催化活性更强，顺序为：dCPe > CPpe > dppp > dppe > dppm，相比之下在CD₂Cl₂中活性较低。所描述的五种膦配体系统的活性均低于基于bcope（其中bcope为(C₈H₁₄)PCH₂–CH₂P(C₈H₁₄)）和tbucope（其中tbucope为(C₈H₁₄)PC₆H₄CH₂P(tBu)₂）的系统。检测到顺-顺-1,2,3,4-四苯基-丁-1,3-二烯作为次要反应产物，同时Pd(LL′)(PhCH–CHPh–CPhCHPh)⁺（4）在炔烃二聚化步骤中也显示出作用。