1σ(4),2σ(2)-diphosphete | 172266-61-4

• 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: 1σ(4),2σ(2)-diphosphete
• 英文别名: 3-tert-butyl-1-N,1-N,1-N',1-N'-tetra(propan-2-yl)-4-trimethylsilyl-1lambda5,2-diphosphacyclobuta-1,3-diene-1,1-diamine；3-tert-butyl-1-N,1-N,1-N',1-N'-tetra(propan-2-yl)-4-trimethylsilyl-1λ5,2-diphosphacyclobuta-1,3-diene-1,1-diamine
• CAS: 172266-61-4
• 化学式: C₂₁H₄₆N₂P₂Si
• 分子量: 416.643
• InChiKey: RYTJWWANASAQMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.08
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1σ(4),2σ(2)-diphosphete 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Sanchez, Muriel; Reau, Regis; Dahan, Francoise, Angewandte Chemie, 1996, vol. 108, # 19, p. 2386 - 2388

  摘要：

  DOI：
• 作为产物：
  描述：

  2,2-二甲基丙基次基膦 、 (bis(diisopropylamino)phosphanyl)(trimethylsilyl)diazomethane 以 乙醚 为溶剂， 反应 5.0h， 以90%的产率得到1σ(4),2σ(2)-diphosphete
  参考文献：
  名称：

  1σ⁴,2σ^x-Diphosphetes (x = 2−6):  On the Persistence of the P−P Bond

  摘要：

  Irradiation of [bis(diisopropylamino)phosphino] (trimethylsilyl)diazomethane at 254 nm in the presence of tert-butylphosphaalkyne leads to 1 sigma(4),2 sigma(2)-diphosphete 1 in 90% yield. Derivative 1 reacts with Fe-2(CO)(9) and W(CO)(5)(THF) giving rise to the corresponding eta(1)-complexes 2 (48% yield) and 3 (75% yield), respectively. When 1 equiv of methyl trifluoromethanesulfonate and elemental selenium is added to derivative 1, the cationic and neutral 1 sigma(4),2 sigma(3)-diphosphetes 4 and 5 are isolated in 95 and 66% yields, respectively. Addition of 2 equiv of elemental selenium and bis(trimethylsilyl)peroxide to diphosphete 1 gave rise to 1 sigma(4),2 sigma(4)-diphosphetes 6 (43% yield) and 7 (84% yield), respectively. eta(1)-(1 sigma(4),2 sigma(2)-Diphosphete)tungsten complex 3 reacted with bis(trimethylsilyl)peroxide affording heterocyclic complex 8 (68% yield). Addition of 1 equiv of tetrachloro-o-benzoquinone (TCBQ) to the cationic 1 sigma(4),2 sigma(3)-diphosphete 4 and of 2 equiv to the 1 sigma(4),2 sigma(2)-diphosphete 1 affords the 1 sigma(4),2 sigma(5)- and 1 sigma(4),2 sigma(6)-diphosphetes 9 (86% yield) and 10 (92% yield), respectively. Addition of TCBQ to the eta(1)-(1 sigma(4),2 sigma(2)-diphosphete)tungsten complex 3 affords the eta(1)-(1 sigma(4),2 sigma(4)-diphosphete)complex 11 (88% yield), which reacts with 2 equiv of trimethylphosphine leading to the zwitterionic 1 sigma(4),2 sigma(3)-diphosphete 12 (46% yield). Cleavage of the Si-C bond of complex 3 with 1 equiv of tetrabutylammonium fluoride hydrate gives eta(1)-(1 sigma(4),2 sigma(2)-diphosphete)complex 13 (61% yield), which reacts with TCBQ leading to the cis-1,2-diphosphino alkene complex 14 (77% yield). These results demonstrate that the unsaturated four-membered ring skeleton is a remarkable template for inducing unusual P-P interactions. However, the presence of two very bulky substituents on the ethylenic moiety is necessary for the persistence of the cyclic structure, when the two phosphorus atoms feature a high coordination state. Single crystal X-ray diffraction studies of derivatives 7 and 11-14 have been carried out.

  DOI：

  10.1021/ja971821f

文献信息

• From 2-Phosphino-2H-Phosphirene to 1-Phosphino-1H-Phosphirene, 1λ5,2λ3-Diphosphete, and 1,2-Dihydro-1λ3,2λ3-Diphosphete: an Experimental and Theoretical Study
  作者：Muriel Sanchez、Régis Réau、Colin J. Marsden、Manfred Regitz、Guy Bertrand

  DOI：10.1002/(sici)1521-3765(19990104)5:1<274::aid-chem274>3.0.co;2-p

  日期：1999.1.4

  The [bis(diisopropylamino)-phosphino](trimethylsilyl)carbene 4 reacts cleanly with tert-butylphosphaalkyne 2 to give 2-phosphino-2H-phosphirene 5, which was spectroscopically characterized. Heterocycle 5 is thermally unstable and quantitatively rearranges after 3 h at room temperature into the 1 lambda(5),2 lambda(3)-diphosphete 3. Irradiation of 5 at room temperature (lambda = 254 nm) with a Rayonnet photochemical reactor produces 1-phosphino-1H-phosphirene 6 (10%), 1,2-dihydrodiphosphete 7 (3%), and diphosphete 3 (87%). Irradiation of 3 with a high pressure mercury lamp at lambda = 254 nm affords the dihydrodiphosphete 7, which was isolated in 69% yield. Calculations carried out on heterocycles 3 and 5-7 emphasize the crucial effect the amino substituents have on the stability of lambda(5)-phosphacyclobutadiene derivatives, and show that the intrinsic difference in the thermodynamic stability between 1H and 2H-phosphirenes is rather small (68 kJ mol(-1)).
• Armbrust, Ralph; Sanchez, Muriel; Réau, Régis, Journal of the American Chemical Society, 1995, vol. 117, # 43, p. 10785 - 10786
  作者：Armbrust, Ralph、Sanchez, Muriel、Réau, Régis、Bergsträsser, Uwe、Regitz, Manfred、Bertrand, Guy

  DOI：——

  日期：——
• Sanchez, Muriel; Reau, Regis; Dahan, Francoise, Angewandte Chemie, 1996, vol. 108, # 19, p. 2386 - 2388
  作者：Sanchez, Muriel、Reau, Regis、Dahan, Francoise、Regitz, Manfred、Bertrand, Guy

  DOI：——

  日期：——
• 1σ⁴,2σ<i>^x</i>-Diphosphetes (<i>x</i> = 2−6):  On the Persistence of the P−P Bond
  作者：Muriel Sanchez、Régis Réau、Heinz Gornitzka、Françoise Dahan、Manfred Regitz、Guy Bertrand

  DOI：10.1021/ja971821f

  日期：1997.10.1

  Irradiation of [bis(diisopropylamino)phosphino] (trimethylsilyl)diazomethane at 254 nm in the presence of tert-butylphosphaalkyne leads to 1 sigma(4),2 sigma(2)-diphosphete 1 in 90% yield. Derivative 1 reacts with Fe-2(CO)(9) and W(CO)(5)(THF) giving rise to the corresponding eta(1)-complexes 2 (48% yield) and 3 (75% yield), respectively. When 1 equiv of methyl trifluoromethanesulfonate and elemental selenium is added to derivative 1, the cationic and neutral 1 sigma(4),2 sigma(3)-diphosphetes 4 and 5 are isolated in 95 and 66% yields, respectively. Addition of 2 equiv of elemental selenium and bis(trimethylsilyl)peroxide to diphosphete 1 gave rise to 1 sigma(4),2 sigma(4)-diphosphetes 6 (43% yield) and 7 (84% yield), respectively. eta(1)-(1 sigma(4),2 sigma(2)-Diphosphete)tungsten complex 3 reacted with bis(trimethylsilyl)peroxide affording heterocyclic complex 8 (68% yield). Addition of 1 equiv of tetrachloro-o-benzoquinone (TCBQ) to the cationic 1 sigma(4),2 sigma(3)-diphosphete 4 and of 2 equiv to the 1 sigma(4),2 sigma(2)-diphosphete 1 affords the 1 sigma(4),2 sigma(5)- and 1 sigma(4),2 sigma(6)-diphosphetes 9 (86% yield) and 10 (92% yield), respectively. Addition of TCBQ to the eta(1)-(1 sigma(4),2 sigma(2)-diphosphete)tungsten complex 3 affords the eta(1)-(1 sigma(4),2 sigma(4)-diphosphete)complex 11 (88% yield), which reacts with 2 equiv of trimethylphosphine leading to the zwitterionic 1 sigma(4),2 sigma(3)-diphosphete 12 (46% yield). Cleavage of the Si-C bond of complex 3 with 1 equiv of tetrabutylammonium fluoride hydrate gives eta(1)-(1 sigma(4),2 sigma(2)-diphosphete)complex 13 (61% yield), which reacts with TCBQ leading to the cis-1,2-diphosphino alkene complex 14 (77% yield). These results demonstrate that the unsaturated four-membered ring skeleton is a remarkable template for inducing unusual P-P interactions. However, the presence of two very bulky substituents on the ethylenic moiety is necessary for the persistence of the cyclic structure, when the two phosphorus atoms feature a high coordination state. Single crystal X-ray diffraction studies of derivatives 7 and 11-14 have been carried out.