tris-((di-i-propylamino)phosphoxane) | 74563-07-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环化合物
• 英文名称: tris-((di-i-propylamino)phosphoxane)
• 英文别名: 2-N,2-N,4-N,4-N,6-N,6-N-hexa(propan-2-yl)-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-triamine
• CAS: 74563-07-8
• 化学式: C₁₈H₄₂N₃O₃P₃
• 分子量: 441.471
• InChiKey: NRKOFWDLMKBIIR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  二氯(去菠二烯)铂(II) 、 tris-((di-i-propylamino)phosphoxane) 以 正己烷 为溶剂， 以75%的产率得到
  参考文献：
  名称：

  Metal-Assisted Formation of Phosphorus-Oxygen Heterocyclic Complexes

  摘要：

  Starting with bis(dialkylamino)phosphine oxides or triphosphoxane [R(2)NPO](3) rings, transition metal complexes containing P4O4, P5O5, and P6O6 heterocycles have been assembled. Specific products isolated were found to depend critically on reaction conditions, the metal, and its ancillary ligands, as well as the phosphorus substituent. While only monometallic products were obtained from divalent precursors of the nickel triad, bimetallic complexes were also produced from the group 6 metal carbonyls. In general, larger rings were obtained at higher temperatures. Only P3O3 and P4O4 products were formed around molybdenum, while P5O5 structures could also be assembled about chromium, nickel, palladium, and platinum centers. One of the iron carbonyl complexes was found to feature an unusual eta(1)-P[OP(O)]P-2 ring, the product of a double POP to PP(=O) rearrangement. In addition, a dichromium P6O6 cluster complex featuring the novel hexaphosphoxane ring was synthesized from bis(cis-2,6-dimethylpiperidino)phosphine oxide. Use of isolated monometallic PnOn complexes as ligands yielded heterobimetallic products as well as phosphoxane ring transfer reactions. The X-ray crystal structures of five representative complexes containing FeP4O4 (14), Cr2P4O4 (19a, 19b), Cr2P6O6 (21), and MoFeP4O4, (25) cores, respectively, are reported.

  DOI：

  10.1021/om00001a017
• 作为产物：
  描述：

  二氯-N,N-二异丙基亚磷酰胺 在 lithium oxide 作用下， 以 四氢呋喃 为溶剂， 反应 504.0h， 以53%的产率得到tris-((di-i-propylamino)phosphoxane)
  参考文献：
  名称：

  Quin, Louis D.; Ionkin, Alexey S., Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 103, # 1-4, p. 205 - 214

  摘要：

  DOI：

文献信息

• Co-ordinated cyclo-tetraphosphosxane and cyclo-pentaphosphoxane; two configurations of the co-ordinated P4O4 ring
  作者：Edward H. Wong、Eric J. Gabe、Florence L. Lee

  DOI：10.1039/c39890001236

  日期：——

  cis-M(CO)4[Pri2NPO]4, which contains both chair–boat and chair–chair forms of the co-ordinated P4O4 ring in solution as well as in the molecular structure; additional products of the chromium reactoin include the chromium cage complex, Cr2(CO)8[Pri2NPO]4, and Cr2(CO)7[Pri2NPO]5 which contains the novel cyclo-pentaphosphoxane P5O5 ring co-ordinated to one cis-Cr(CO)4 and one fac-Cr(CO)3 moiety.

  六羰基铬的热反应或-钨与二钼（CO）的（二-异丙基氨基）氧化膦或光解6与[镨我2 NPO] 3，得到顺式-M（CO）4 [镨我2 NPO] 4，其中包含溶液和分子结构中配位的P 4 O 4环的椅子-船形和椅子-椅子形式；铬反应蛋白的其他产物包括铬笼络合物，Cr 2（CO）8 [Pr i 2 NPO] 4和Cr 2（CO）7[镨我2 NPO] 5含有新颖环-pentaphosphoxane P 5 ø 5环协调到一个CIS -Cr（CO）4和一个FAC -Cr（CO）3部分。
• A metal complex of 2,4,6-tris(N,N-di-isopropylamino)cyclotriphosphoxane that is an intermediate to the P4O4M2 cage complex
  作者：Edward H. Wong、Eric J. Gabe、Jean-Pierre Charland

  DOI：10.1039/c39880001632

  日期：——

  Reaction of (Pri2N)2P(O)H with Mo(CO)6 gives the title compound (2) identified as a Mo(CO)5 complex of the six-membered [Pri2NPO]3 heterocycle and found to be an intermediate for the formation of the P4O4M2 cage complex.

  （Pr i 2 N）2 P（O）H与Mo（CO）6的反应得到标题化合物（2），该化合物鉴定为六元[Pr i 2 NPO] 3杂环的Mo（CO）5配合物，被发现是形成P 4 O 4 M 2笼络合物的中间体。
• Niecke, Edgar; Zorn, Hans; Krebs, Bernt, Angewandte Chemie, 1980, vol. 92, # 9, p. 737 - 738
  作者：Niecke, Edgar、Zorn, Hans、Krebs, Bernt、Henkel, Gerald

  DOI：——

  日期：——
• Metal-Assisted Formation of Phosphorus-Oxygen Heterocyclic Complexes
  作者：Xiaoyong Sun、Edward H. Wong、Mark M. Turnbull、Arnold L. Rheingold、Beth E. Waltermire、Robert L. Ostrander

  DOI：10.1021/om00001a017

  日期：1995.1

  Starting with bis(dialkylamino)phosphine oxides or triphosphoxane [R(2)NPO](3) rings, transition metal complexes containing P4O4, P5O5, and P6O6 heterocycles have been assembled. Specific products isolated were found to depend critically on reaction conditions, the metal, and its ancillary ligands, as well as the phosphorus substituent. While only monometallic products were obtained from divalent precursors of the nickel triad, bimetallic complexes were also produced from the group 6 metal carbonyls. In general, larger rings were obtained at higher temperatures. Only P3O3 and P4O4 products were formed around molybdenum, while P5O5 structures could also be assembled about chromium, nickel, palladium, and platinum centers. One of the iron carbonyl complexes was found to feature an unusual eta(1)-P[OP(O)]P-2 ring, the product of a double POP to PP(=O) rearrangement. In addition, a dichromium P6O6 cluster complex featuring the novel hexaphosphoxane ring was synthesized from bis(cis-2,6-dimethylpiperidino)phosphine oxide. Use of isolated monometallic PnOn complexes as ligands yielded heterobimetallic products as well as phosphoxane ring transfer reactions. The X-ray crystal structures of five representative complexes containing FeP4O4 (14), Cr2P4O4 (19a, 19b), Cr2P6O6 (21), and MoFeP4O4, (25) cores, respectively, are reported.
• Coordination complexes derived from tri-, tetra-, and pentaphosphoxane rings
  作者：Edward H. Wong、Xiaoyong Sun、Eric J. Gabe、Florence L. Lee、Jean Pierre Charland

  DOI：10.1021/om00055a011

  日期：1991.9

  Thermal reactions of hexacarbonylchromium and -tungsten with bis(diisopropylamino)phosphine oxide yielded the tetraphosphoxane complexes cis-M(CO)4[(i)Pr2NPO]4 as the major products. Spectral data and X-ray structural determination of the molybdenum analogue confirmed 1,5-coordination of statistical mixtures of the chair-boat (C(S)) and chair-chair (C2-upsilon) conformations of the P4O4 ring. Crystal data: monoclinic, A2/a; a = 18.992 (1), b = 11.306 (5), c = 19.368 (1) angstrom; beta = 98.63 (1)-degrees; V = 4111.6 (4) angstrom 3; Z = 4; final R(F) = 0.062, R(wF) = 0.057 for 2219 significant reflections and varying 204 parameters. Minor coproducts from the chromium reaction included Cr2(CO)8[(i)Pr2NPO]4, with a tetradentate P4O4 ring chelating both metals, as well as Cr2(CO)7[(i)Pr2NPO]5. The latter structure features a novel pentaphosphoxane P5O5 ring coordinated to one Cr(CO)3 and one Cr(CO)4 to form a bimetallic cage. Crystal data: monoclinic, P2(1)/c; a = 12.6554 (8), b = 17.639 (1), c = 23.670 (1) angstrom; beta = 101.82 (1)-degrees; V = 5171.7 (5) angstrom 3; Z = 4; final R(F) = 0.088, R(wF) = 0.081 for 4337 significant reflections and varying 491 parameters. Under milder reaction conditions with molybdenum hexacarbonyl, a triphosphoxane complex Mo(CO)5[(i)Pr2NPO]3 can be isolated. Crystal data: orthorhombic, Pbc2(1); a = 11.570 (2), b = 18.729 (5), c = 32.056 (3) angstrom; V = 6946.36 angstrom 3; Z = 8; final R(F) = 0.047, R(wF) = 0.048 for 3469 significant reflections and varying 685 parameters. This was converted readily by heating to the known Mo2(CO)8[(i)Pr2NPO]4 cage complex. Reactions of the parent [(i)Pr2NPO]3 triphosphoxane ring with Mo(CO)4(norbornadiene) afforded a 1:1 complex cis-Mo(CO)4-[(i)Pr2NPO]3 which also transformed into the same adamantanoid cage complex upon warming. With bis(benzonitrile)palladium dichloride, triphosphoxane gave a product characterized by spectral data and X-ray crystallography to be cis-PdCl2[(i)Pr2NPO]4 with a 1,5-coordinated tetraphosphoxane ring exclusively in the chair-chair (C2-upsilon) conformation. Crystal data: monoclinic C2/c; a = 19.980 (5), b = 11.0945 (10), c = 17.934 (9) angstrom; beta = 112.04 (3)-degrees; V = 3684.8 angstrom 3; Z = 4; final R(w) = 0.051 and R(wF) = 0.060 for 252 variables using 3246 significant reflections. A similar reaction with NiBr2.DME (DME = dimethoxyethane) yielded instead a 1,3-coordinated P4O4 complex NiBr2[(i)Pr2NPO]4. The parent [(i)Pr2NPO]4 ligand, stable below -20-degrees-C, can be liberated from this Ni complex by pyridine substitution. It reverts to the triphosphoxane compound upon warming to ambient temperature.