三苯基膦高氯酸盐 | 76021-76-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 三苯基膦高氯酸盐
• 英文名称: Ph3P*HClO4
• 英文别名: triphenyl-phosphine; perchlorate；Triphenyl-phosphin; Perchlorat；Perchloric acid;triphenylphosphane；perchloric acid;triphenylphosphane
• CAS: 76021-76-6
• 化学式: C₁₈H₁₆P*ClO₄
• 分子量: 362.749
• InChiKey: FIWXTHWTRAKBFA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.58
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  74.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  粪甾烷-3-醇 、 三苯基膦高氯酸盐 以 二氯甲烷 为溶剂， 以60%的产率得到
  参考文献：
  名称：

  Electrochemical Preparation and Some Reactions of Alkoxy Triphenylphosphonium Ions.

  摘要：

  重新研究了在醇存在下通过阳极氧化 Ph3 P 形成烷氧基三苯基鏻离子。当 Ph3P、Ph3P+H·ClO-4 和醇的 CH2CL2 溶液在配有石墨阳极和 Pt 阴极的整体电解槽中进行恒流电解时，所得电解液的 31P-NMR 谱表明烷氧基三苯基鏻高氯酸盐 (2) 由脂肪伯醇和仲脂肪醇以良好到中等的产率形成，而烯丙醇和苄醇转化为相应的烷基磷鎓离子，并且在脂肪族叔醇的情况下，没有形成相应的烷氧基或烷基磷鎓离子离子完全被识别。通过简单的程序以良好的产率实现了由此形成的2的分离。对于电解，可以使用Ph3P+H·BF-4代替高氯酸盐，由伯和仲脂肪醇得到烷氧基三苯基鏻四氟硼酸盐(3)。研究了由β-和α-胆甾烷醇制备的烷氧基鏻离子与Bu4N+·X-（X=Br、Cl、F、N3、SCN）、PhSH和PhOH等各种亲核试剂的反应。结果表明，鏻离子的反应位点由亲核试剂的特性决定。软亲核试剂易于攻击α-碳，以良好的产率生成相应的SN2反应产物，而硬亲核试剂则易于攻击磷鎓离子的磷，从而导致胆甾烷醇的再生。

  DOI：

  10.1248/cpb.43.1076
• 作为试剂：
  描述：

  正癸酸 在 三苯基膦高氯酸盐 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到癸醛
  参考文献：
  名称：

  One-Step Transformation of Carboxylic Acids into Aldehydes Induced by the Electrochemical Oxidation of Ph3P.

  摘要：

  在氮气气氛下，使用一室电解槽以及两个石墨板作为阳极和阴极，对Ph3P和羧酸（RCO2H，1）在CH2Cl2中进行恒电流电解（CCE）时，当使用Ph3P+H·ClO-4作为支持电解质时，得到了相应的醛（2）。部分还原受到电解条件选择的影响，特别是温度和电流密度，这取决于1的结构。因此，在-30°C下进行的CCE反应，R=Ph-、o-Cl-Ph-、p-MeO-Ph-、Ph(CH2)2-、CH3(CH2)8-以及Ph2CH的1均顺利进行，获得了良好的产率。而对于R=cyclo-C6H11-和(CH3)2CH-的1，则需要在回流条件下进行电解，且对于R=(CH3)3C-的情况，醛的产率即使在回流下也很低。基于在分隔电池中通过CCE得到的CH2Cl2溶液中Ph3P、Ph3P+H·ClO-4和1的循环伏安分析结果，提出了部分还原的顺序为：阳极上形成酰氧基三苯基膦离子（3）；3与Ph3P反应生成相应的酰基三苯基膦离子（4）；在阴极上将4还原为α-羟基烷基三苯基膦离子（7）；在CCE后经过水相处理时，7分解为2和Ph3P。伏安研究还表明，3转化为4的难易程度反映在所需的CCE条件中，可能决定了2的产率。

  DOI：

  10.1248/cpb.42.1041

文献信息

• Attempts To Prepare Palladium(II) Complexes with the O,C,O Pincer Aryl Ligand C₆(NO₂)₂-2,6-(OMe)₃-3,4,5
  作者：José Vicente、Aurelia Arcas、Miguel-Angel Blasco、José Lozano、M. Carmen Ramírez de Arellano

  DOI：10.1021/om980633a

  日期：1998.11.1

  = C6(NO2)2-2,6-(OMe)3-3,4,5-C1 (2)), obtained by thermal decomposition of [Hg(O2CR)2] (1), reacts with Q2[Pd2Cl4(μ-Cl)2] to give [Hg(R)Cl] (3) and Q2[Pd(R)Cl(μ-Cl)]2 (Q = (PhCH2)Ph3P (4a), Me4N (4b)), which react (i) with Tl(acac) (1:2, acac = acetylacetonate) to give Q[Pd(R)Cl(O,O-acac)] (Q = (PhCH2)Ph3P (5a), Me4N (5b)) or (ii) with AgClO4 (1:2) to give [Pd(κ3-R)Cl] (κ3-R = κ3-C6(NO2)2-2,6-(OMe)3-3

  通过[Hg（O 2 CR ）的热分解获得的络合物[HgR 2 ]（R = C 6（NO 2）2 -2,6-（OMe）3 -3,4,5-C 1（2）））2 ]（1），与Q 2 [Pd 2 Cl 4（μ-Cl）2 ]反应，得到[Hg（R）Cl]（3）和Q 2 [Pd（R）Cl（μ-Cl）] 2（Q =（PhCH 2）Ph 3 P（4a），Me 4 N（4b））），将（i）与Tl（acac）（1：2，acac =乙酰丙酮化物）反应，得到Q [Pd（R）Cl（O，O-acac）]（Q =（PhCH 2）Ph 3 P（图5a）中，Me 4 N（图5b））或（ii）与AgClO 4（1：2），得到[钯（κ 3 -R）CL]（κ 3 -R =κ 3 -C 6（NO 2）2 -2,6-（OMe）3 -3,4,5-C 1，O，O'（6）），也可以通过5a与HBF 4反应获得。配合物6与对甲苯胺（1：1，L）
• Polynuclear platinum phosphanido/phosphinito complexes: formation of P–O and P–O–P bonds through reductive coupling processes
  作者：Irene Ara、Juan Forniés、Susana Ibáñez、Piero Mastrorilli、Stefano Todisco、Vito Gallo

  DOI：10.1039/c5dt02593a

  日期：——

  complexes [(C6F5)2Pt(μ-PPh2)(μ-PPh2O)Pt(μ-PPh2)2Pt(dppm)] (2) or [NBu4]2[(C6F5)2Pt(μ-PPh2)(μ-PPh2O)Pt(μ-PPh2)2Pt(μ-Cl)2Pt(μ-PPh2)2Pt(μ-PPh2)(μ-PPh2O)Pt(C6F5)2] (as a mixture of the two possible isomers 4a and 4b). Complex 2 reacts with AgClO4 to form the tetranuclear derivative [(C6F5)2Pt(μ-PPh2)(μ-PPh2O)Pt(μ-PPh2)2Pt(dppm)Ag(OClO3)] (3), which displays two Pt–Ag donor–acceptor bonds. The mixture of the hexanuclear

  式的不对称配合物的混合物[（R ˚F）2铂（μ-PH 2 PO）（μ-PPH 2）的Pt（μ-PPH 2）2的Pt（SOLV）（SOLV'）] [（1 - （ SOLV）（SOLV '）]（SOLV，SOLV'=丙酮，H 2 O，CH 3 CN）已经制备由[（R的反应˚F）2的Pt II（μ-PPH 2）2的Pt II（μ-PPH 2）2 Pt II（NCCH 3）2 ]和CH 3中的AgClO 4CN /丙酮。对该Pt溶剂键的不稳定性可通过DPPM或Cl协调溶剂分子的位移-和三-或六核phosphanido的隔离/ phosphinito的Pt（II）络合物[（C 6 ˚F 5）2的Pt（μ- PPH 2）（μ-PPH 2 O）的Pt（μ-PPH 2）2的Pt（DPPM）]（2）或[NBU 4 ] 2 [（C 6 ˚F 5）2铂（μ-PPH 2）（μ- PPH 2 O）的Pt（μ-PPH
• Vicente, Jose; Chicote, Maria-Teresa; Bermudez, Maria-Dolores, Journal of Chemical Research - Part S
  作者：Vicente, Jose、Chicote, Maria-Teresa、Bermudez, Maria-Dolores、Jones, Peter G.、Sheldrick, George M.

  DOI：——

  日期：——
• Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C₆F₅)₂Pt(μ-PPh₂)₂Pt(μ-PPh₂)₂Pt(PPh₃)]
  作者：Juan Forniés、Consuelo Fortuño、Susana Ibáñez、Antonio Martín、Piero Mastrorilli、Vito Gallo、Athanassios Tsipis

  DOI：10.1021/ic3021639

  日期：2013.2.18

  The reaction of [NBu4][(C6F5)(2)Pt(mu-PPh2)(2)Pt(mu-PPh2)(2)Pt(O,O-acac)] (48 VEC) with [HPPh3][ClO4] gives the 46 VEC unsaturated [(C6F5)(2)Pt-1(mu-PPh2)(2)Pt-2(mu-PPh2)(2)Pt-3(PPh3)](Pt-2-Pt-3) (1), a trinuclear compound endowed with a Pt-Pt bond. This compound displays amphiphilic behavior and reacts easily with nucleophiles L, yielding the saturated complexes [(C6F5)(2)Pt-II(mu-PPh2)(2)Pt-II(mu-PPh2)(2)Pt-II(PPh3)L] [L = PPh3 (2), py (3)]. The reaction with the electrophile [Ag(OClO3)PPh3] affords the adduct 1 center dot AgPPh3, which evolves, even at low temperature, to a mixture in which [(C6F5)(2)Pt-III(mu-PPh2)(2)Pt-III(mu-PPh2)(2)Pt-II(PPh3)(2)](2+)(Pt-III-Pt-III) and 2 (plus silver metal) are present. The nucleophilic nature of 1 is also demonstrated through its reaction with cis-[Pt(C6F5)(2)(THF)(2)], which results in the formation of [Pt-4(mu-PPh2)(4)(C6F5)(4)(PPh3)] (4). The structure indicate that 1 can be better considered as a Pt-II-Pt-III-Pt-I complex instead of a Pt-II-Pt-II-Pt-II derivative. Theoretical calculations (density functional theory) on similar model compounds are in agreement with the assigned oxidation states of the metal centers. The strong intermetallic interactions resulting in a Pt-2-Pt-3 metal metal bond and the respective bonding mechanism were verified by employing a multitude of computational techniques (natural bond order analysis, the Laplacian of the electron density, and localized orbital locator profiles).
• Electrochemical Preparation and Some Reactions of Alkoxy Triphenylphosphonium Ions.
  作者：Hatsuo MAEDA、Takashi KOIDE、Toshihide MAKI、Hidenobu OHMORI

  DOI：10.1248/cpb.43.1076

  日期：——

  The formation of an alkoxy triphenylphosphonium ion by anodic oxidation of Ph3 P in the presence of an alcohol was reinvestigated. When a CH2CL2 solution of Ph3P, Ph3P+H·ClO-4, and an alcohol was subjected to constantcurrent electrolysis in an undivided cell equipped with a graphite anode and a Pt cathode, the 31P-NMR spectra of the resulting electrolyte showed that alkoxy triphenylphosphonium perchlorates (2) were formed in good to fair yields from primary and secondary aliphatic alcohols, while allylic and benzylic alcohols were transformed to the correspinding alkyl phosphonium ions, and in the case of tertiary aliphatic alcohols, no formation of the corresponding alkoxy or alkyl phosphonium ions was recognized at all. The isolation of 2 thus formed was achieved in good yields by a simple procedure. For the electrolysis, Ph3P+H·BF-4 could be utilized insted of the perchlorate salt, giving an alkoxy triphenylphosphonium tetrafluoroborate (3) from primary and secondary aliphatic alcohols. The reaction of the alkoxy phosphonium ions prepared from β- and α-cholestanol with various nucleophiles such as Bu4N+·X- (X=Br, Cl, F, N3, SCN), PhSH, and PhOH was examined. The results indicated that the reaction site of the phosphonium ions is dictated by the identity of the nucleophile. A soft nucleophile was apt to attack at the α-carbon, giving the corresponding SN2 reaction product in a good yield, while a hard one tended to react at the phosphorus of the phosphonium ion, leading to the regeneration of the cholestanol.

  重新研究了在醇存在下通过阳极氧化 Ph3 P 形成烷氧基三苯基鏻离子。当 Ph3P、Ph3P+H·ClO-4 和醇的 CH2CL2 溶液在配有石墨阳极和 Pt 阴极的整体电解槽中进行恒流电解时，所得电解液的 31P-NMR 谱表明烷氧基三苯基鏻高氯酸盐 (2) 由脂肪伯醇和仲脂肪醇以良好到中等的产率形成，而烯丙醇和苄醇转化为相应的烷基磷鎓离子，并且在脂肪族叔醇的情况下，没有形成相应的烷氧基或烷基磷鎓离子离子完全被识别。通过简单的程序以良好的产率实现了由此形成的2的分离。对于电解，可以使用Ph3P+H·BF-4代替高氯酸盐，由伯和仲脂肪醇得到烷氧基三苯基鏻四氟硼酸盐(3)。研究了由β-和α-胆甾烷醇制备的烷氧基鏻离子与Bu4N+·X-（X=Br、Cl、F、N3、SCN）、PhSH和PhOH等各种亲核试剂的反应。结果表明，鏻离子的反应位点由亲核试剂的特性决定。软亲核试剂易于攻击α-碳，以良好的产率生成相应的SN2反应产物，而硬亲核试剂则易于攻击磷鎓离子的磷，从而导致胆甾烷醇的再生。