Tri-isopropylsilylphosphan | 147237-79-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Tri-isopropylsilylphosphan
• 英文别名: tri-iso-propylsilylphosphane；tri(isopropyl)silylphosphine；H2PSi(iPr)3；Tri(propan-2-yl)silylphosphane
• CAS: 147237-79-4
• 化学式: C₉H₂₃PSi
• 分子量: 190.341
• InChiKey: HWRFVMBCUGCWNV-UHFFFAOYSA-N

物化性质

• 沸点：
  206.8±9.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.04
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  Tri-isopropylsilylphosphan 以 正庚烷 为溶剂， 生成
  参考文献：
  名称：

  新型环状笼状铟磷铟砷化合物的合成与表征

  摘要：

  DOI：

  10.1002/1521-3749(200211)628:11<2255::aid-zaac2255>3.0.co;2-#
• 作为产物：
  描述：

  三异丙基氯硅烷 在 三氯化铝 、 二氢磷化锂 作用下， 以 乙二醇二甲醚 为溶剂， 反应 48.0h， 以90%的产率得到Tri-isopropylsilylphosphan
  参考文献：
  名称：

  Synthesis of the Bifunctional Phosphinidene Cluster, Fe₃(CO)₉(μ₃-PH)₂, and a Systematic Study of the Reactivity of the Cluster-Bound P−H Functional Group

  摘要：

  The synthesis and systematic study of the reaction chemistry of a bifunctional phosphinidene cluster, Fe-3(CO)(9)(mu(3)-PH)(2) (3) is reported. Reaction chemistry at one P-H functional site is effectively communicated through the Fe-3(CO)(9) core, and impacts on the reactivity of the second P-H site. Deprotonation of the acidic protons in 3 allows access to a lone electron pair on phosphorus, The first proton is readily removed with NEt3/[PPN]Cl ([PPN](+) = (Ph3P)(2)N+) to produce the [PPN](+) salt of [Fe-3(CO)(9)(mu(3)-PH)(mu(3)-P)(-) ([4](-)) Removal of both phosphorus-bound hydrogen atoms in 3 requires the use of 2 equiv of n-BuLi, to produce Li-2[Fe-3(CO)(9)(mu(3)-P)(2)] (Li-2[5]). Quenching of Li-2[5] with MeOH-d(4) generates [Fe-3(CO)(9)(mu(3)-PD)(mu(3)-P)](-). The lone electron pairs on the cluster-bound phosphorus atoms undergo analogous reaction chemistry to organophosphines. Alkylation at the phosphorus site is carried out by reaction of [Et3NH][4] with MeOSO2CF3 generating the monosubstituted cluster, Fe-3(CO)(9)(mu(3)-PMe)(mu(3)-PH) (6) as the primary product, The cluster anions [4](-) and [8](-), containing a phosphorus lone pair, are oxidized by elemental sulfur to produce the phosphine sulfide complexes, [Et3NH][Fe-3(CO)(9)(mu(3)-PH)(mu(3)-P=S)] ([Et3NH][10]) and [Et3NH][Fe-3(CO)(9)(mu(3)-PMe)(mu(3)-P=S)] ([Et-3-NH][11]). Treatment of [10](-) with an additional equivalent of NEt3 and S-8 yields the dianionic cluster, [Et-3-NH](2)[Fe-3(Co)(9)(mu(3)-P=S)(2)] ([Et3NH](2)[12]). Without added base, reaction of the neutral clusters, 3 and 6, with S-8 in THF solution yield the clusters Fe-3(CO)(9)(mu(3)-PH)(mu(3)-PSCH2CH2CH2CH2OH) (13), Fe-3(CO)(9)(mu(3)-PSCH2-CH2CH2CH2OH)(2) (14), and Fe-3(CO)(9)(mu(3)-PMe)(mu(3)-PSCH2CH2CH2CH2OH) (15), with a ring-opened THF molecule appended to sulfur. Reaction of 3 with Ss in THF solution in the presence of ClAuPPh3 produces the gold derivative, Fe-3(CO)(9)(mu(3)-PSAuPPh3)(2) (17). Like PH groups in phosphines, the mu(3)-PH moieties in 3 react with activated alkenes to yield single- and double-insertion products, Fe-3(CO)(9)(mu(3)-PH)(mu(3)-PCH2CH2R) (R = CN (18a), CO2Me (19a)) and Fe-3(CO)(9)(mu(3)-PCH2CH2R)(2) (R = CN (18b), Co2Me (19b)). The solid-state structures of 3, 17, and 18b were determined by single-crystal X-ray diffraction.

  DOI：

  10.1021/ja993811f

文献信息

• Oxidative Addition Reactions of Low‐Valent Gallium Compounds with Primary Phosphanes
  作者：Selina Schneider、Carsten Hänisch

  DOI：10.1002/ejic.202100723

  日期：2021.12.7

  Reactions of different primary phosphanes with the Ga(I) compound (Dipp2NacNac)Ga were investigated and show surprising differences in reactivity depending on the solvent and the substituent bond to phosphorus.

  研究了不同伯膦与 Ga(I) 化合物 (Dipp 2 NacNac)Ga 的反应，并显示出令人惊讶的反应性差异，具体取决于溶剂和与磷的取代基键。
• Synthesis and Characterisation of Novel Main Group Element Clusters with Tin‐Phosphorus, Tin‐Arsenic, and Germanium‐Phosphorus Skeletons
  作者：Donna Nikolova、Carsten von Hänisch、Ariane Adolf

  DOI：10.1002/ejic.200300744

  日期：2004.6

  with iPr3SiPLi2 to give [Ge6(PSiiPr3)6] (5). Compounds 1−5 were characterised by NMR and IR spectroscopic techniques as well as elemental analysis. The crystal structures were identified by X-ray diffraction analysis, which confirmed that the heptameric skeletons of 1 and 2 are structurally analogous. The Sn/P cluster 3 contains subvalent tin atoms, while 4 forms a Sn4As6Li4 rhombododecahedron and 5 a

  iPr3SiPLi2 与 SnCl2 以 1:1 的摩尔比反应形成 [Sn7(PSiiPr3)7] (1)。如果用略微过量的金属盐进行相同的反应，则获得簇 [Sn8(PSiiPr3)6Cl2](3​​)。SnCl2 和 iPr3SiAsLi2 之间以 1:1 和 2:3 的摩尔比进行类似的氯化锂消除反应，然而，产生 [Sn7(AsSiiPr3)7] (2) 和 [Sn4(AsSiiPr3)6Li4(Et2O)2] (4)，分别。金属盐 GeCl2(diox)2 (diox = 1,4-dioxane) 与 iPr3SiPLi2 反应生成 [Ge6(PSiiPr3)6] (5)。化合物 1-5 通过 NMR 和 IR 光谱技术以及元素分析进行​​表征。通过 X 射线衍射分析鉴定了晶体结构，这证实了 1 和 2 的七聚体骨架在结构上是相似的。Sn/P 簇 3 含有亚价锡原子，而 4 形成一个 Sn4As6Li4
• From Dinuclear Zirconium(+3)‐Phosphido Complexes {[Cp ₂ ZrP(H)R] ₂ } to the First Neutral Zirconocene–Phosphinidene Dimers [(Cp ₂ ZrPR) ₂ ] by P–H Dehydrogenation
  作者：Matthias Driess、Joachim Aust、Klaus Merz

  DOI：10.1002/ejic.200400820

  日期：2005.3

  H-combustion analyses. The molecular structures of 3a and 3c were additionally confirmed by X-ray crystal structure analyses, showing that they consist of Zr2P2 rings with significantly shorter Zr–P distances than those observed in 1a and 1c. Interestingly, the dehydrogenation of the mostly sterically crowded derivative 1c occurs also in boiling toluene solutions without using a catalyst, but the process is

  新型锆(+3)甲硅烷基膦基配合物[Cp2ZrP(H)R]2} 1a Cp = η5-C5H5; 报道了 R = SiMe2C(iPr)Me2}、1b (R = SiiPr3) 和 1c (R = SiF(tBu)(2,4,6-iPr3C6H2)。后者很容易通过锂盐的反应获得相应的初级甲硅烷基膦与施瓦茨试剂 [Cp2Zr(H)Cl] 在 –70 °C 的 THF 中。它们可以以抗磁性红黑色晶体的形式以 68–85% 的产率分离。配合物的中心结构基序由平面 (1a, 1b) 和略微褶皱的 Zr2P2 环 (1c) 组成，并包含两个 d1-Zr(+3) 中心，它们是反铁磁耦合的（超级交换，通过键相互作用），尽管跨环 Zr-Zr 分离是大约 360 pm。因此，这些化合物具有双自由基电子结构。在 Pd/C 或 [(Ph3P)2Pt(C2H4)] 存在下加热 1a-c 在甲苯中的溶液导致 P-H
• NMR-spektroskopische und strukturelle charakterisierung der tri-iso-propylsilylphosphanide des calciums
  作者：Matthias Westerhausen、Ralph Löw、Wolfgang Schwarz

  DOI：10.1016/0022-328x(95)05971-q

  日期：1996.5

  In the presence of bis[bis-(trimethylsilyl)amino]stannylene hetero-bi-metallic pentakis(THF)dicalcium-tin(II)-bis(tri-iso-propylsilylphosphanide)-bis(tri-iso-propylsilylphosphandiide) 6 can be isolated; in this derivative the calcium atoms are sixfold, the phosphorus atoms quadruple and the tin atoms threefold coordinated (triclinic, , a = 1654.4(1), b = 2137.3(2), c = 2170.6(2) pm, α= 82.285(7), β

  （1,2-二甲氧基- O，O'）的反应锂phosphanide与氯三异-propylsilane产量三-异-propylsilylphosphane 1以及双（三-异丙-propylsilyl）膦2。从正戊烷溶液中重结晶可得到2（单斜晶，P 2 1 / c，a = 1510.5（1），b = 771.18（5），c = 2033.4（1）pm，β = 108.972（6）°的单晶，Z = 4，wR 2 = 0.0947）。1的化学计量双[双（三甲基甲硅烷基）酰胺]钙决定了产品的组成。等摩尔比导致二聚（1,2-二甲氧基- O，O'）钡，双（三甲硅烷基）酰胺-三-异-propylsilylphosphanide 3与终端氨基配体和桥接phosphanido取代基（单斜晶系，P 2 1 / ç，一个= 1073.8（2），b＝ 1267.7（3），c＝ 2228.8（4）pm，β＝ 100.03°，Z＝
• Cage Compounds of Phosphorus and the Heavier Group 14 Elements
  作者：Stefan Almstätter、Miriam Eberl、Gábor Balázs、Michael Bodensteiner、Manfred Scheer

  DOI：10.1002/zaac.201200116

  日期：2012.9

  The Sn/P cage compounds [Sn10(tBuP)4] (1) and [Sn10(tBuP)7Cl4] (2) were obtained by the reaction of LitBuPH with SnBr2 and SnCl2, respectively. Theoretical calculations confirm that the tin atoms in 2 feature different formal oxidation states. The reaction of PbCl2 with LitBuPH and LiPHSiiPr3 yields the Pb/P cage compounds [Pb7(tBuP)7] (3) and [Pb6(PSiiPr3)6] (4), respectively, that represent new derivatives

  Sn/P 笼化合物 [Sn10(tBuP)4] (1) 和 [Sn10(tBuP)7Cl4] (2) 分别通过 LitBuPH 与 SnBr2 和 SnCl2 的反应获得。理论计算证实 2 中的锡原子具有不同的形式氧化态。PbCl2 与 LitBuPH 和 LiPHSiiPr3 的反应分别产生 Pb/P 笼化合物 [Pb7(tBuP)7] (3) 和 [Pb6(PSiiPr3)6] (4)，它们代表了此类已知多面体的新衍生物化合物。新产品通过 X 射线衍射、元素分析和部分 MS 和 MAS-NMR 光谱表征。