bis(triphenyl-λ⁵-phosphanylidene)ammonium hydrogen sulfate | 136598-96-4

• 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: bis(triphenyl-λ⁵-phosphanylidene)ammonium hydrogen sulfate
• 英文别名: Bis(triphenylphosphoranylidene) Ammonium Hydrogen Sulfate；Bis(triphenyl-lambda5-phosphanylidene)azanium;hydrogen sulfate；bis(triphenyl-λ5-phosphanylidene)azanium;hydrogen sulfate
• CAS: 136598-96-4
• 化学式: C₃₆H₃₀NP₂*HO₄S
• 分子量: 635.66
• InChiKey: OZVVGYXEDLPITJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.41
• 重原子数：
  44
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  86.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(triphenyl-λ⁵-phosphanylidene)ammonium hydrogen sulfate 、 (tetra(n-butyl)ammonium) trans-di(cyano)phthalocyaninato(1-)rhenate(III) 以 二氯甲烷 为溶剂， 生成 bis(triphenylphosphine)iminium trans-di(cyano)phthalocyaninato(1-)rhenate(III)
  参考文献：
  名称：

  （自旋简并）反式二（氰基）酞菁酸盐的共振电子和振动拉曼光谱中的构型内、三重态和异常极化的 A 1g 和 A 2g 跃迁

  摘要：

  棕色双（四（正丁基）铵）反式二（氰基）酞菁（2-）铼（II）（1）是通过将双（酞菁（2-）铼（II））与四（正）-丁基）氰化铵。与电化学数据一致，用碘氧化 1 得到蓝色四（正丁基）铵反式二（氰基）酞菁（2-）铼酸盐（III）（2），其阳离子超过双（三苯基膦）亚胺-盐，如 X 射线结构分析所证实。1和2溶于浓。硫酸，用冰水稀释后从硫酸中沉淀出蓝色的反式二（氰基）酞菁（2-）铼（III）酸。1和2被溴氧化成紫色的反式二（氰基）酞菁（1-）铼（III）。描述了用过氧化二苯甲酰和N-氯代琥珀酰亚胺进行的氧化。图 1 和 2 的特征在于偏振共振拉曼 (RR)、FIR/MIR 和 UV-Vis-NIR 光谱。由于低自旋 ReII 的 Kramers 简并基态，在 1 的 RR 光谱中观察到完全对称振动 a1g 在 598 和 672 cm–1 处的极化异常，去极化度 ρl > 3。在不寻常的紫外-Vis-NIR

  DOI：

  10.1002/1521-3749(200008)626:8<1803::aid-zaac1803>3.0.co;2-#
• 作为产物：
  描述：

  双(三苯基正膦基)氯化铵 在 potassium hydrogensulfate 作用下， 以 水 为溶剂， 以78%的产率得到bis(triphenyl-λ⁵-phosphanylidene)ammonium hydrogen sulfate
  参考文献：
  名称：

  Temperature- and solvate-dependent disorder in the crystal structure of [PNP]⁺[HSO₄]⁻

  摘要：

  摘要：[PNP]Cl ([PNP]⁺ ≡ 双三苯基-λ-五磷杂氮离子)与Na₂[SO₄]或K[HSO₄]在水中发生交换反应，分别生成无色固体[PNP]₂[SO₄]和[PNP][HSO₄]。在碱性条件下，[PNP]⁺阳离子会部分分解。核磁共振光谱鉴定出N-二苯基膦-三苯基磷氮，三苯基膦亚胺和苯为分解产物。[PNP]₂[SO₄]和[PNP][HSO₄]化合物通过多核核磁共振和振动光谱进行表征。[PNP][HSO₄]可以从乙腈-二乙醚中结晶出单晶体，其中含有额外的乙腈溶剂分子和不含有乙腈溶剂分子的单晶体。在两种结构中，[HSO₄]⁻阴离子在固态中形成二聚体，由O-H⋯O氢键保持在一起。在温度为127 K时，不含溶剂的[PNP][HSO₄]晶体结构中的[HSO₄]⁻阴离子是有序的，而在温度为300 K且含有额外乙腈溶剂分子的结构中，[HSO₄]⁻阴离子的两个位置上观察到无序状态，后者甚至在150 K时也是如此。

  DOI：

  10.1515/znb-2019-0016

文献信息

• Simple Ion–Gas Mixtures as a Source of Key Molecules Relevant to Prebiotic Chemistry
  作者：Samuel Paula、Liam S. Goulding、Katherine N. Robertson、Jason A. C. Clyburne

  DOI：10.3390/molecules26237394

  日期：——

  of key prebiotic inorganic molecules. The two reactions investigated here involve such simple systems, (a) carbon disulfide (CS2) and acetate (CH3COO¯) and (b) sulfur dioxide (SO2) and formate (HCOO¯). They have been carried out under non-aqueous conditions, either in an organic solvent or with a powdered salt exposed to the requisite gas. Under such dry conditions the first reaction generated the thioacetate

  非常简单的化学反应可以快速、高产地生产关键的益生元无机分子。这里研究的两个反应涉及这样简单的系统，(a) 二硫化碳 (CS 2 ) 和醋酸盐 (CH 3 COO¯) 和 (b) 二氧化硫 (SO 2 ) 和甲酸盐 (HCOO¯)。它们是在非水条件下进行的，可以是在有机溶剂中，也可以是将粉状盐暴露在必要的气体中。在这种干燥条件下，第一个反应生成硫代乙酸根阴离子 [CH 3 COS]¯，而第二个反应生成自由基 [SO 2 ·]¯阴离子。无水条件并不罕见，可能出现在早期地球上可以产生不同相（液体/气体或固体/气体）之间界面的地方。这是使益生元世界所必需的分子和离子（如我们已产生）的形成合理化的一种方法。对我们结果的解释提供了对与更突出的生物发生理论一致的情景的洞察。
• Thermoformable, thermosettable epoxy/polyester reaction products
  申请人：THE DOW CHEMICAL COMPANY

  公开号：EP0417601A2

  公开（公告）日：1991-03-20

  Thermoformable, thermosettable resins essentially free of secondary alcohol groups are obtained by reaction of oxiranes in active hydrogen-free epoxies with carboxylate or carbonate groups in active hydrogen-free aryl polyesters, polycarbonates or copolyestercarbonates in the presence of catalytically effective amounts of certain polyorgano phosphonium or phosphine imminium salts.

  活性无氢环氧树脂中的环氧乙烷与活性无氢芳基聚酯、聚碳酸酯或共聚酯碳酸酯中的羧酸酯或碳酸酯基团在催化有效量的某些多有机膦盐或膦铱盐存在下反应，可获得基本上不含仲醇基团的可热成型的热沉性树脂。
• Mononitrosyl- undtrans-Dinitrosyl-Komplexe von Phthalocyaninaten des Mangans und Rheniums
  作者：Melanie Göldner、Bärbel Geniffke、Andreas Franken、Keith S. Murray、Heiner Homborg

  DOI：10.1002/1521-3749(200105)627:5<935::aid-zaac935>3.0.co;2-j

  日期：2001.5

  Tetra(n-butyl)ammonium or di(triphenylphosphane)iminium nitrosylacidophthalocyaninato(2-)manganate, (cat)[Mn(NO)(X)pc(2-)] (X = ONO, NCO, N-3: cat = (Bu4N)-Bu-n, PNP) is prepared from acidophthalocyaninato(2-)manganese, [Mn(X)pc(2-)], (cat)NO2 and ((Bu4N)-Bu-n)BH4 in CH2Cl2 or from nitrosylphthalocyaninato(2-)manganese. [Mn(NO)pc(2-)] and ((Bu4N)-Bu-n)X (X = ONO, NCO, N-3, NCS) at T < 120 degreesC. respectively. [Mn(NO)(X)pc(2-)](-) dissociates in methanol. and [Mn(NO)pc2-] precipitates. Nitrito(O)phthalocyaninato(2-)manganese, (cat)NO2 and hydrogensulfide yield trans-di(nitrosyl)phthalocyaninato(2-)manganate. (trans)[Mn(NO)(2)pc(2-)](-) isolated as red violet (PNP) and ((Bu4N)-Bu-n) complex salt. Nitrosyl(triphenylphosphane oxide)phthalocyaninato(2-)manganese, [Mn(NO)(OPPh3)pc(2-)] is obtained by addition of OPPh3 to [Mn(NO)pc(2-)] at 200 degreesC. Di(triphenylphosphane)phthalocyaninato(2-)rhenium(II) and (PNP)NO2 in CH2Cl2 or in molten (PNP)NO2 and PPh3 at 100 degreesC yields green blue l-di( triphenylphosphane) iminium nitrosylnitrito(O)phthalocyaninato(2-)rhenate. (l)(PNP)[Re(NO)(ONO)pc2-]. Similarly, but with ((Bu4N)-Bu-n)NO2 red plates of tetra-(n-butyl) ammonium trans-di(nitrosyl)phthalocyaninato(2-)rhenate, ((Bu4N)-Bu-n)(trans)[Re(NO)(2)pc(2-)] is isolated. Addition of (PNP)Br or (PNP)PF6 to a concentrated solution of ((Bu4N)-Bu-n)(trans)[Re (NO)(2)pc(2-)] in pyridine precipitates (l)(PNP)(trans)[Re(NO)(2)pc(2-)]. ((Bu4N)-Bu-n)(trans)[Re(NO)(2)pc(2-)] and PPh3 at 300 degreesC yield blue green nitrosyl(triphenylphosphane oxide)phthalocyaninato(2-)rhenium, [Re(NO)(OPPh3)pc2-], that is oxidised with iodine precipitating nitrosyl(triphenylphosphane oxide)phthalocyaninato(2-)rhenium triiodide, [Re(NO)(OPPh3)pc(2-)]I-3. The crystal structures of (l)(PNP)[Mn(NO)(ONO)pc(2-)] (1), (l)(PNP)[Mn(NO)(NCO)pc(2-)] (2), (l)(PNP)(trans)[Mn(NO)(2)pc(2-)] (3),l(PNP)(trans)[Re(NO)(2)pc(2-)] (4) [Mn(NO)(OPPh3)pc(2-)] (5), [Re(NO)(OPPh3)pc(2-)] (6), and [Re(NO)(OPPh3)pc(2-)]I-3. CH2Cl2 (7) have been determined. The M-N(NO) distance varies between 1.623(12)Angstrom in 5 and 1.846(3)Angstrom in 3. The M-N-O moiety is almost linear. The UV-Vis spectra with the B band at ca. 14500 cm(-1) and the Q band at 30400 cm(-1) do not dependent significantly on the axial ligand and the metal atom and its oxidation state. N-O stretching vibrations are observed in the IR spectra between 1701 cm(-1) in 3 and 1753 cm(-1) in [Mn(NO)pc(2-)] or for the Re series between 1571 cm(-1) in 4 and 1724 cm(-1) in 7. M-N(NO) stretching and M-N-O deformation vibrations are assigned in the IR spectra and resonance Raman spectra between 486 cm(-1) in 4 and 620 cm(-1) in 1.
• Darstellung und Eigenschaften vontrans-Di(fluoro)phthalocyaninato(2-)-rhenat(III); Kristallstruktur deslinear-Bis(triphenylphosphin)iminium-Doppelsalzesl(PNP)trans[Re(F)2pc2-] · 0,33l(PNP)F · 2 H2O
  作者：Melanie Göldner、Heiner Hückstädt、Heiner Homborg

  DOI：10.1002/(sici)1521-3749(199805)624:5<897::aid-zaac897>3.0.co;2-s

  日期：1998.5

  trans-Bis(triphenylphosphine)phthalocyanato (2-)rhenium(II) reacts with ((Bu4N)-Bu-n)F . 3H(2)O in acetone on air yielding trans-di(fluoro)phthalocyaninato(2-)rhenate(III), (trans)[Re(F)(2)pc(2-)](-). The complex anion is precipitated as tetra(n-butyl)ammonium ((Bu4N)-Bu-n), or after addition of (PNP)HSO4 as linear-bis(triphenylphosphine)iminium ((l)(PNP)) salt. The latter crystallizes as a double salt of formula (l)(PNP)(trans)[Re(F)(2)pc(2-)]. 0.33(l)(PNP)F . 2H(2)O in the cubic space group I23 (no.197) with the cell parameter a = 21.836(2) Angstrom; V = 10412(2) Angstrom(3); Z = 6. The Re atom is located in the centre of the (N-iso)(4) plane (N-iso: isoindole-N atom) and coordinates axially two fluorine atoms in a mutual trans position. The Re-N and Re-F distance is 2.035(6) and 1.798(7) Angstrom, respectively. According to the short Re-F distance the asymmetric Re-F stretching vibration is observed in the MIR spectrum at 746 cm(-1). Obviously due to a large spin-orbit coupling, the complex salt with an electronic low-spin d(4) ground state of Re-III (S = 1) is diamagnetic. Hence a sharp signal is observed at -126.1 ppm in the (FNMR)-F-19 spectrum. The UV-VIS-NIR spectrum shows the typical pi-pi* transitions at 15000 (B), 29500 (Q) and 36900 cm(-1) (N) and trip-multiplet transitions at 9500/10500 cm(-1) and 13200/14100 cm(-1).
• US5037903A
  申请人：——

  公开号：US5037903A

  公开（公告）日：1991-08-06