tris(triphenylstannyl)phosphine | 13371-33-0

• 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: tris(triphenylstannyl)phosphine
• CAS: 13371-33-0
• 化学式: C₅₄H₄₅PSn₃
• 分子量: 1081.06
• InChiKey: QDMBCXBYHUWMNL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.47
• 重原子数：
  58.0
• 可旋转键数：
  12.0
• 环数：
  9.0
• 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：

  tris(triphenylstannyl)phosphine 、 六羰基铬 以 further solvent(s) 为溶剂， 生成 (CO)5CrP{Sn(C₆H₅)3}3
  参考文献：
  名称：

  Stelzer, O.; Niederreuther, U., 4th Intern. Conf. Organometal. Chem., Bristol 1969, S. U 5

  摘要：

  DOI：
• 作为产物：
  描述：

  三苯基氯化锡 在 1,3-dicyano-5-fluoro-2,4,6-tris(diphenylamino)benzene 、 四苯基二膦 、 二苯基膦 、 间二溴苄 作用下， 以 乙腈 、 苯 为溶剂， 反应 24.0h， 以56%Spectr.的产率得到tris(triphenylstannyl)phosphine
  参考文献：
  名称：

  不对称膦和鏻盐的多功能可见光驱动合成。

  摘要：

  不对称取代的叔膦和季鏻盐广泛应用于工业界和学术界。尽管它们很重要，但合成此类化合物的经典方法通常需要苛刻的反应条件、起始材料的预官能化、高度敏感的有机金属试剂或昂贵的过渡金属催化剂。因此，尽管目前人们很感兴趣，但温和、实用的方法仍然难以捉摸。在这里，我们描述了一种可见光驱动的方法，由仲膦和伯膦形成这些产品。使用廉价的有机光催化剂和蓝光照射，芳基膦可以使用市售的有机卤化物进行烷基化和芳基化。此外，相同的有机催化剂可用于在单个反应步骤中将白磷（P 4 ）直接转化为对称芳基膦和鏻盐，这在以前只能使用贵金属催化来实现。

  DOI：

  10.1002/chem.202002646

文献信息

• Radical synthesis of trialkyl, triaryl, trisilyl and tristannyl phosphines from P4
  作者：Brandi M. Cossairt、Christopher C. Cummins

  DOI：10.1039/c0nj00124d

  日期：——

  A reaction scheme has been devised according to 3 RX + 3 Ti(III) + 0.25 P4 → PR3 + 3 XTi(IV), wherein RX = PhBr, CyBr, Me3SiI or Ph3SnCl, with contrasting results in the case of more hindered RX. The scheme accomplishes the direct radical functionalization of white phosphorus without the intermediacy of PCl3.

  已设计出一种反应方案：3 RX + 3 Ti(III) + 0.25 P4 → PR3 + 3 XTi(IV)，其中RX = PhBr、CyBr、Me3SiI或Ph3SnCl，针对空间位阻更大的RX情况，反应结果有显著差异。该方案实现了白磷的直接自由基功能化，无需经过PCl3中间体。
• Photocatalytic Arylation of P ₄ and PH ₃ : Reaction Development Through Mechanistic Insight
  作者：Robin Rothfelder、Verena Streitferdt、Ulrich Lennert、Jose Cammarata、Daniel J. Scott、Kirsten Zeitler、Ruth M. Gschwind、Robert Wolf

  DOI：10.1002/anie.202110619

  日期：2021.11.8

  studies provide significant, new insights into the mechanism of the recently reported photocatalytic arylation of white phosphorus (P4). Through the first-time observation of a series of reaction intermediates, these studies have also inspired the development of the first examples of direct, catalytic arylation of PH3, which is a key synthetic intermediate for industrial phosphorus chemistry.

  31 P 1 H} NMR 光谱研究为最近报道的白磷 (P 4 ) 光催化芳基化机制提供了重要的新见解。通过对一系列反应中间体的首次观察，这些研究还启发了 PH 3直接催化芳基化的第一个实例的开发，PH 3 是工业磷化学的关键合成中间体。
• Reactions of Imidazolio‐Phosphides with Organotin Chlorides: Surprisingly Diverse
  作者：Florian Goerigk、Nicholas Birchall、Christoph M. Feil、Martin Nieger、Dietrich Gudat

  DOI：10.1002/ejic.202101026

  日期：2022.3.18

  Reactions of imidazolio-phosphides (“imidazolylidene-phosphinidenes”) with organotin mono- and dihalides follow different reaction channels. DFT studies reveal that the structurally different products observed represent the most stable species under the specific reaction conditions and indicate that the switch between different reaction modes is controlled by the Lewis acidity of the electrophile employed

  咪唑啉磷化物（“咪唑亚膦”）与有机锡单卤化物和二卤化物的反应遵循不同的反应途径。DFT 研究表明，观察到的结构不同的产物代表了特定反应条件下最稳定的物质，并表明不同反应模式之间的切换受所用亲电试剂的路易斯酸度控制。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: Org.Verb., 1.1.2.1.4.2, page 54 - 62
  作者：

  DOI：——

  日期：——
• The Stannylphosphide Anion Reagent Sodium Bis(triphenylstannyl) Phosphide: Synthesis, Structural Characterization, and Reactions with Indium, Tin, and Gold Electrophiles
  作者：Christopher C. Cummins、Chao Huang、Tabitha J. Miller、Markus W. Reintinger、Julia M. Stauber、Isabelle Tannou、Daniel Tofan、Abouzar Toubaei、Alexandra Velian、Gang Wu

  DOI：10.1021/ic403178j

  日期：2014.4.7

  Treatment of P-4 with in situ generated [Na][SnPh3] leads to the formation of the sodium monophosphide [Na][P(SnPh3)(2)] and the Zintl salt [Na](3)[P-7]. The former was isolated in 46% yield as the crystalline salt [Na(benzo-15-crown-5)][P(SnPh3)(2)] and used to prepare the homoleptic phosphine P(SnPh3)(3), isolated in 67% yield, as well as the indium derivative (XL)(2)InP(SnPh3)(2) (XL = S(CH2)(2)NMe2), isolated in 84% yield, and the gold complex (Ph3P)AuP(SnPh3)(2). The compounds [Na(benzo-15-crown-5)][P(SnPh3)(2)], P(SnPh3)(3), (XL)(2)InP(SnPh3)(2), and (Ph3P)AuP(SnPh3)(2) were characterized using multinuclear NMR spectroscopy and X-ray crystallography. The bonding in (Ph3P)AuP(SnPh3)(2) was dissected using natural bond orbital (NBO) methods, in response to the observation from the X-ray crystal structure that the dative P -> Au bond is slightly shorter than the shared electron-pair P-Au bond. The bonding in (XL)(2)InP(SnPh3)(2) was also interrogated using P-31 and C-13 solid-state NMR and computational methods. Co-product [Na](3)[P-7] was isolated in 57% yield as the stannyl heptaphosphide P-7(SnPh3)(3), following salt metathesis with ClSnPh3. Additionally, we report that treatment of P-4 with sodium naphthalenide in dimethoxyethane at 22 degrees C is a convenient and selective method for the independent synthesis of Zintl ion [Na](3)[P-7]. The latter was isolated as the silylated heptaphosphide P-7(SiMe3)(3), in 67% yield, or as the stannyl heptaphosphide P-7(SnPh3)(3) in 65% yield by salt metathesis with ClSiMe3 or ClSnPh3, respectively.