N-lithio-N-tert-butylamino-diphenylphosphane

• 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: N-lithio-N-tert-butylamino-diphenylphosphane
• 英文别名: Lithium diphenylphosphino(t-butyl)amide；lithium;tert-butyl(diphenylphosphanyl)azanide
• 化学式: C₁₆H₁₉NP*Li
• 分子量: 263.248
• InChiKey: AQOFELDQOHOXJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.21
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [bis(trimethylsilyl)methylene]chlorophosphane 、 N-lithio-N-tert-butylamino-diphenylphosphane 以 四氢呋喃 、 正庚烷 、 苯 为溶剂， 以0.387 g的产率得到P-tert-butyl(diphenylphosphanyl)amino-C-bis(trimethylsilyl)phosphaalkene
  参考文献：
  名称：

  Sterically Tuned P -Phosphanylamino Phosphaalkenes (Me₃ Si)₂ C=PN(R )PPh₂ and (i PrMe₂ Si)₂ C=PN(R )PPh₂

  摘要：

  Deprotonation of the aminophosphanes Ph2PN(H)R 1a–1h [R = tBu (1a), 1‐adamantyl (1b), iPr (1c), CPh3 (1d), Ph (1e), 2,4,6‐Me3C6H2 (Mes) (1f), 2,4,6‐tBu3C6H2 (Mes*) (1g), 2,6‐iPr2C6H3 (DIPP) (1h)], followed by reactions of the phosphanylamide salts Li[Ph2PNR] 2a, 2b, 2g, and 2h with the P‐chlorophosphaalkene (Me3Si)2C=PCl, and of 2a–2g with (iPrMe2Si)2C=PCl, gave the isolable P‐phosphanylamino phosphaalkenes (Me3Si)2C=PN(R)PPh2 3a, 3b, 3g, and (iPrMe2Si)2C=PN(R)PPh2 4a–4g. 31P NMR spectra, supported by X‐ray structure determinations, reveal that in compounds 2a, 2b, 3a, and 3b, with bulky N‐alkyl groups the Si2C=P–N–P skeleton is non‐planar (orthogonal conformation), whereas 3g, 3h, and 4g with bulky N‐aryl groups exhibit planar conformations of the Si2C=P–N–P skeleton. Solid 3g and 4g exhibit cisoid orientation of the planar C=P–N–C units (planar I) but in solid 3h the transoid rotamer is present (planar II). From 3g, 4d, and 4g mixtures of rotamers were detected in solution by pairs of 31P NMR patterns (3h: line broadening).

  DOI：

  10.1002/zaac.201700446
• 作为产物：
  描述：

  N-tert-butyl-1,1-diphenylphosphinamine 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.0h， 生成 N-lithio-N-tert-butylamino-diphenylphosphane
  参考文献：
  名称：

  (N-锂硫氨基)二有机膦和双(N-硫氨基)有机膦：合成和结构

  摘要：

  丁基锂 (nBuLi) 在乙醚中使 Ph2P–NHtBu 去质子化，得到 (Ph2P–NLitBu)2·OEt2。在这个分子中没有 Li…P 相互作用。三种 R'P(NLiR)2 类型的化合物已通过 R'P(NHR)2 锂化获得，分离为 [BuP(NLiPh)2·OEt2]2、[PhP(NLiPh)2·OEt2]2 和[PhP(NLiPh)2]2。nBuLi 与 MeP(NHiPr)2 在己烷/THF 中的反应导致 [MeP{N(Li)iPr]2·THF}4 具有不对称簇结构，包括一个 LiP3、三个 LiPN2、三个 LiP2N 和一个 LiN3 簇单元。通过 X 射线结构分析确定的这些化合物的分子结构表明，它们最好被描述为 N-锂硫氨基膦，而不是异构的 P-硫代亚氨基膦。

  DOI：

  10.1002/(sici)1099-0682(199912)1999:12<2355::aid-ejic2355>3.0.co;2-h

文献信息

• (N-lithioamino)diorganophosphanes and Bis(N-Lithioamino)organophosphanes: Synthesis and Structures
  作者：Bettina Eichhorn、Heinrich Nöth、Thomas Seifert

  DOI：10.1002/(sici)1099-0682(199912)1999:12<2355::aid-ejic2355>3.0.co;2-h

  日期：1999.12

  [PhP(NLiPh)2]2. Reaction of nBuLi with MeP(NHiPr)2 in hexane/THF leads to [MePN(Li)iPr]2·THF}4 with an asymmetric cluster structure comprising one LiP3, three LiPN2, three LiP2N and one LiN3 cluster units. The molecular structures of these compounds as determined by X-ray structure analysis show that they are best depicted as N-lithioaminophosphanes and not as the isomeric P-lithioiminophosphoranes.

  丁基锂 (nBuLi) 在乙醚中使 Ph2P–NHtBu 去质子化，得到 (Ph2P–NLitBu)2·OEt2。在这个分子中没有 Li…P 相互作用。三种 R'P(NLiR)2 类型的化合物已通过 R'P(NHR)2 锂化获得，分离为 [BuP(NLiPh)2·OEt2]2、[PhP(NLiPh)2·OEt2]2 和[PhP(NLiPh)2]2。nBuLi 与 MeP(NHiPr)2 在己烷/THF 中的反应导致 [MePN(Li)iPr]2·THF}4 具有不对称簇结构，包括一个 LiP3、三个 LiPN2、三个 LiP2N 和一个 LiN3 簇单元。通过 X 射线结构分析确定的这些化合物的分子结构表明，它们最好被描述为 N-锂硫氨基膦，而不是异构的 P-硫代亚氨基膦。
• Sterically Tuned <i>P</i> -Phosphanylamino Phosphaalkenes (Me₃ Si)₂ C=PN(<i>R</i> )PPh₂ and (<i>i</i> PrMe₂ Si)₂ C=PN(<i>R</i> )PPh₂
  作者：Roxana M. Bîrzoi、Daniela Lungu、Peter G. Jones、Rainer Bartsch、Wolf-W. du Mont

  DOI：10.1002/zaac.201700446

  日期：2018.4.17

  Deprotonation of the aminophosphanes Ph2PN(H)R 1a–1h [R = tBu (1a), 1‐adamantyl (1b), iPr (1c), CPh3 (1d), Ph (1e), 2,4,6‐Me3C6H2 (Mes) (1f), 2,4,6‐tBu3C6H2 (Mes*) (1g), 2,6‐iPr2C6H3 (DIPP) (1h)], followed by reactions of the phosphanylamide salts Li[Ph2PNR] 2a, 2b, 2g, and 2h with the P‐chlorophosphaalkene (Me3Si)2C=PCl, and of 2a–2g with (iPrMe2Si)2C=PCl, gave the isolable P‐phosphanylamino phosphaalkenes (Me3Si)2C=PN(R)PPh2 3a, 3b, 3g, and (iPrMe2Si)2C=PN(R)PPh2 4a–4g. 31P NMR spectra, supported by X‐ray structure determinations, reveal that in compounds 2a, 2b, 3a, and 3b, with bulky N‐alkyl groups the Si2C=P–N–P skeleton is non‐planar (orthogonal conformation), whereas 3g, 3h, and 4g with bulky N‐aryl groups exhibit planar conformations of the Si2C=P–N–P skeleton. Solid 3g and 4g exhibit cisoid orientation of the planar C=P–N–C units (planar I) but in solid 3h the transoid rotamer is present (planar II). From 3g, 4d, and 4g mixtures of rotamers were detected in solution by pairs of 31P NMR patterns (3h: line broadening).