(Adamant-1-yl-trimethylsiloxy)-methylidene-trimethylsilylphosphine | 156568-65-9

• 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: (Adamant-1-yl-trimethylsiloxy)-methylidene-trimethylsilylphosphine
• 英文别名: (Z)-(Adamant-1-yl-trimethylsiloxy)-methylidene-trimethylsilylphosphine；(E)-(Adamant-1-yl-trimethylsiloxy)-methylidene-trimethylsilylphosphine；((adamantyl)(Me3SiO)CP(SiMe3))；[1-Adamantyl(trimethylsilyloxy)methylidene]-trimethylsilylphosphane
• CAS: 156568-65-9
• 化学式: C₁₇H₃₃OPSi₂
• 分子量: 340.593
• InChiKey: CBQPVKQLKXYNGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.97
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Adamant-1-yl-trimethylsiloxy)-methylidene-trimethylsilylphosphine 在 NaH 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 {μ-((adamantyl)(Me3SiO)HCPH)B5H8}(1-)
  参考文献：
  名称：

  小型杂硼烷簇系统。2.小​​硼烷笼与低配位磷化合物的反应制备磷硼烷体系：磷烯烃与五硼烷的反应化学（9）

  摘要：

  The reaction of (Me3Si)P = C(R)(OSiMe3) (where R = tert-butyl (1a) or adamantyl (1b) with 1 equiv of neutral pentaborane(9), B5H9, under mild conditions produces the synthetically versatile, small bridging phosphaboranes [mu-((R)(Me3SiO)HCP(SiMe3))B5H8] (2a,b) in excellent yields. Two possible mechanisms for the formation of 2a and 2b by this reaction are supported by both experimental and MNDO semiempirical theoretical data. These relatively thermal and air-stable compounds are also stable with respect to the elimination of Me3SiOSiMe3. They are quantitatively converted, however, to [mu-((R)(Me3SiO)CHP(X))B5H8] (where X = H (3a,b) and X = D (4a,b)) by electrophilic substitution reactions with water, D2O, or alcohol. Compound 2a is readily bridge-deprotonated by the action of NaH to produce the corresponding anion, [mu-((tert-butyl)(Me3SiO)CHP(SiMe3))B5H7]- (5a), while 2b is unreactive under similar conditions. Compound 5a was found to be unreactive toward metal cations in complex formation. Compound 3a slowly loses H-2 on standing at room temperature to form the bridged P = C system, [mu-((tert-butyl)(Me3SiO)C = P)B5H8] (6a). Compound 3a is readily cage-deprotonated to form the corresponding anion, [mu-((tert-butyl)-(Me3SiO)CHP(H))B5H7]- (7a), which, when reacted with metal halides, forms metallaphosphaborane complexes. Data from MNDO calculations for compounds 2a, 3a, 5a, and 6a show linear relationships between the calculated charge on the bridgehead boron atoms and both the phosphorus-apical boron bond distance and the bridgehead basal boron bond centroid-phosphorus-carbon bond angle. These trends have been rationalized by using semiempirical molecular orbital considerations. Characterization of the new compounds was by H-1, B-11, C-13, and P-31 NMR, infrared, mass spectral, and elemental analyses.

  DOI：

  10.1021/om00050a057
• 作为产物：
  描述：

  1-Adamantoyl-bisphosphine 以 环戊烷 为溶剂， 反应 0.25h， 生成 (Adamant-1-yl-trimethylsiloxy)-methylidene-trimethylsilylphosphine
  参考文献：
  名称：

  Unusually Coordinated Phosphorus Compounds; 7¹. Adamant-1-ylmethylidynephosphine, A New, Stable Phosphaalkyne

  摘要：

  三[三甲基硅基]膦 (4a) 以及双[三甲基硅基]膦锂四氢呋喃络合物 (4b) 与 1- 金刚烷酰氯 (5) 反应生成膦烃 7，收率分别为 67% 或 96%。随后，在 20/90 ℃条件下，用氢氧化钠或四正丁基氟化铵催化消除 7 中的六甲基二硅氧烷，得到膦炔 8，收率分别为 83% 或 71%。膦炔 8 与 1,3-二极（如氧化腈 9、重氮化合物 12a-c 和叠氮化物 15）发生平滑的 [3 + 2] 环加成反应，分别生成膦孔 11、14a-c 和 16。膦烯 7 与偶极 9 和 12a 反应，分别生成相同的环加成物 11 和 14a。在这两个反应中，初级加合物会自发（10 → 11）或在氢氧化钠催化下（13 → 14a）消除六甲基二硅氧烷。

  DOI：

  10.1055/s-1986-31467

文献信息

• Examination of Indium Triphospholyls as Precursors for Nanoparticle Synthesis
  作者：Reinhard Rund、Susanne Bauer、Andreas Stauber、Michael Seidl、Wilfried‐Solo Ojo、Fabio Ferrari、Bruno Chaudret、Céline Nayral、Fabien Delpech、Manfred Scheer

  DOI：10.1002/ejic.202001100

  日期：2021.3.19

  described. Further, the synthesis of indium nanoparticles via a single‐source precursor approach using In(1,2,4‐P3C2tBu2) (1) as precursor is reported. These nanoparticles were characterized by TEM, HRTEM, EDX, XRD, NMR, and optical spectroscopy.

  新化合物K（P 3 C 2 R 2）[R = Ad（2），s Bu（3）]和In（P 3 C 2 R 2）[R = Ad（4），Mes的合成和表征（（5）]被描述。此外，还报道了使用In（1,2,4-P 3 C 2 t Bu 2）（1）作为前体的单源前体方法合成铟纳米粒子。这些纳米颗粒通过TEM，HRTEM，EDX，XRD，NMR和光谱进行表征。
• Goerlich, Jens R.; Mueller, Christian; Schmutzler, Reinhard, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 85, # 1-4, p. 193 - 206
  作者：Goerlich, Jens R.、Mueller, Christian、Schmutzler, Reinhard

  DOI：——

  日期：——
• Breit, Bernhard; Regitz, Manfred, Chemische Berichte, 1993, vol. 126, # 8, p. 1945 - 1950
  作者：Breit, Bernhard、Regitz, Manfred

  DOI：——

  日期：——
• Regitz, M.; Heydt, H.; Wagner, O., Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 49/50, p. 341 - 344
  作者：Regitz, M.、Heydt, H.、Wagner, O.、Schnurr, W.、Ehle, M.、Hoffmann, J.

  DOI：——

  日期：——
• ALLSPACH, T.;REGITZ, M.;BECKER, G.;BECKER, W., SYNTHESIS, BRD, 1986, N 1, 31-36
  作者：ALLSPACH, T.、REGITZ, M.、BECKER, G.、BECKER, W.

  DOI：——

  日期：——