N,N-Bis(trimethylsilyl)aminodiphenylphosphan | 13685-61-5

• 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,N-Bis(trimethylsilyl)aminodiphenylphosphan
• 英文别名: Ph2PN(SiMe3)2；P,P-Diphenyl-N,N-bis-trimethylsilyl-phosphinamid；Bis(trimethylsilyl)amino-diphenylphosphin；[[bis(trimethylsilyl)amino]-phenylphosphanyl]benzene
• CAS: 13685-61-5
• 化学式: C₁₈H₂₈NPSi₂
• 分子量: 345.572
• InChiKey: DDUIHHFSQJCECX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.01
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  N,N-Bis(trimethylsilyl)aminodiphenylphosphan 在 正丁基锂 、 溴 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 6.0h， 生成
  参考文献：
  名称：

  [（o-RCHC6H4）PPh2 = NSiMe3]-（R = H，SiMe3）配体的锂配合物的合成，结构和反应。

  摘要：

  通过Ph2P（Br）= NSiMe3与邻甲基苯基锂反应制得N-三甲基甲硅烷基邻甲基苯基二苯基膦亚胺（o-MeC6H4）PPh2 = NSiMe3（1）。用LiBun处理1，然后用Me3SiCl处理，得到（o-Me3SiCH2C6H4）PPh2 = NSiMe3（2）。在tmen存在下用LiBu（n）进行1和2的锂化反应得到结晶锂络合物[Li {CH（R）C6H4（PPh（2 = NSiMe3）-。tmen]（3，R = H; 4，R =从4的母液中，得到痕量的经tmen桥连的络合物[Li {CH（SiMe3）C6H4（PPh2 = NSiMe3）-2}] 2（mu-tmen）（5），使2与在Et2O中的LiBun生成络合物[Li {CH（SiMe3）C6H4（PPh2 = NSiMe3）-2} .OEt2]（6）。锂与Me2SiCl2以2：1摩尔比反应，得到二甲基甲硅烷基桥接的化合物Me2Si

  DOI：

  10.1039/b418389d
• 作为产物：
  描述：

  二苯基氯化膦 、 lithium hexamethyldisilazane 以 正己烷 为溶剂， 以92%的产率得到N,N-Bis(trimethylsilyl)aminodiphenylphosphan
  参考文献：
  名称：

  具有庞大氨基的氨基膦：分子结构、偶联常数 1J(31P,15N) 和 2J(31P,29Si) 和同位素诱导的化学位移 1Δ14/15N(31P)

  摘要：

  具有大氨基 (1-20) 的氨基膦的优选构象是通过溶液中的 NMR 光谱确定的，在两种情况下为固态 (11,17)，在一种情况下 (11) 通过 X 射线晶体学。三甲基甲硅烷基氨基二苯基膦 Ph2PN(R)SiMe3 (R = Bu (1), Ph (2), 2-吡啶基 (3), 2-嘧啶基 (4), Me3Si (5)), 氨基(氯)苯基膦 Ph(Cl)PNRR' (R = Bz, R' = Me (6), R = Bz, R' = tBu (7), R = Et, R' = Ph (8)), 氨基(氯)叔丁基膦 tBu(Cl)PNRR ' (R = R' = iPr (9), R = Me, R' = tBu (10), R = Bz, R' = tBu (11), R = H, R' = tBu (12), R = Et, R' = Ph (13), R = iPr, R' = Ph

  DOI：

  10.1002/hc.10084

文献信息

• N-Phosphorylated Imidazolium Salts as Precursors to 2- and 5-Phosphorylated Imidazoles and New Imidazol-2-ylidenes Featuring the PNCN Unit
  作者：Anatolii P. Marchenko、Heorgii N. Koidan、Anastasiya N. Huryeva、Evgeniy V. Zarudnitskii、Aleksandr A. Yurchenko、Aleksandr N. Kostyuk

  DOI：10.1021/jo101177h

  日期：2010.11.5

  It has been experimentally proven that the reaction of 1- or 1,2-disubstituted imidazoles with diorganylphosphorus(III) halides proceeds via initial formation of N-phosporylated imidazolium salts. Treatment of these salts with strong bases results in phosphorylation of the parent imidazoles at the 2- or 5-positions, correspondingly. In a previous case, imidazol-2-ylidenes are formed as intermediates

  实验已经证明1-或1，2-二取代的咪唑与二有机基磷（III）卤化物的反应是通过最初形成N-磷酸化的咪唑鎓盐而进行的。用强碱处理这些盐会相应地导致母体咪唑在2或5位发生磷酸化。在先前的情况下，形成咪唑-2-亚基作为中间体。在N1和N3原子上都带有空间要求或/和π供体基团的情况下，将1,3-二取代的咪唑鎓盐与NaN（SiMe 3）2进行去质子化反应可得到新的稳定的N-磷取代的Arduengo型卡宾。
• Preparation and characterization of diarylphosphazene and diarylphosphinohydrazide complexes of titanium, tungsten and ruthenium and phosphorylketimido complexes of rhenium
  作者：Andrew R. Cowley、Jonathan R. Dilworth、Alison K. Nairn、Alasdair J. Robbie

  DOI：10.1039/b417068g

  日期：——

  phosphorylketimido ligand. It is bound to the rhenium centre with a virtually linear Re-N-C arrangement (Re-N-C angle = 176.6 degrees, when X = Cl) and there is multiple bonding between Re and N (Re-N = 1.809(7) A when X = Cl). The proligand Ph2PNHNMe2(L2H) reacts with [(C5H5)TiCl3] to give [(C5H5)TiCl2(Me2NNPPh2)] (6). An X-ray crystal structure of the complex shows the ligand (L2) is bound by both nitrogen

  配体Ph2PN（SiMe3）2（L1）与WCl6反应得到低聚磷腈配合物[WCl4（NPPh2）] n，1，随后与PMe2Ph或NBu4Cl反应得到[WCl4（NPPh2）（PMe2Ph）]（2）或[ WCl5（NPPh2）] [NBu4]（3）。在[WCl5（NPPh2）] [NBu4]上的DF计算表明，W = N双键（1.756 A），PN键距离为1.701 A，这与P原子的几何形状相结合，表明没有PN多重键。L1与MeCN中的[ReOX3（PPh3）2]反应（X = Cl或Br）得到[ReX2（NC（CH3）P（O）Ph2）（MeCN）（PPh3）]（X = Cl，4，X = Br，5），其中含有新的磷酸基酮亚胺基配体。它通过几乎线性的Re-NC排列（Re-NC角度= 176.6度，当X = Cl时）绑定到the中心，并且Re和N之间存在多重键合（当X时Re-N = 1.809（7）A
• Synthesis of Poly(alkyl/arylphosphazenes) via the Ambient Temperature Phosphite-Mediated Chain-Growth Polycondensation of (<i>N</i>-Silyl)bromophosphoranimines
  作者：Thomas J. Taylor、Alejandro Presa Soto、Keith Huynh、Alan J. Lough、Anthony C. Swain、Nicholas C. Norman、Christopher A. Russell、Ian Manners

  DOI：10.1021/ma100876z

  日期：2010.9.28

  polymerizations were complete within 18 h. The polymers prepared include poly(dialkylphosphazenes) (e.g., [nBu2P═N]n1b), poly(alkylarylphosphazenes) (e.g., [PhMeP═N]n1d), new materials featuring unsaturated substituents (e.g., [nHexH2C═C(H)CH2}P═N]n1n), and random copolymers (e.g., [PhMeP═N]x−[PhnBuP═N]y} where x:y = 2:1, 7a). The precursor silylaminophosphines RR′P−N(SiMe3)2 (5a−q) and bromo(silylamino)phosphoranimines

  室温加入化学计算量的亚磷酸三甲酯，P（OME）的3，以ñ -甲硅烷（卤代）organophosphoraniminesBrRR'P═NSiMe 3中导致直接形成高分子量聚磷腈的[RR'P═N氯化溶剂] n。大多数聚合反应在18小时内完成。制备的聚合物包括聚（dialkylphosphazenes）（例如，[ Ñ卜2 P = N] Ñ 1B），聚（alkylarylphosphazenes）（例如，[PhMeP═N] Ñ 1D），新材料设有不饱和取代基（例如，[ Ñ十六进制H 2 C = C（H）CH 2 } P = N] ñ1N），和无规共聚物（例如，[PhMeP═N] X - [PH Ñ BuP═N] ý }其中X：Ý = 2：1，图7a）。前体silylaminophosphines RR'P-N（森达3）2（5A - q）和溴（甲硅烷）phosphoraniminesBrRR'P═NSiMe
• Fine Tuning of the Substituents on the N-Geminal Phosphorus/Silicon-Based Lewis Pairs for the Synthesis of <i>Z</i>-Type Silyliminophosphoranylalkenes
  作者：Jiancheng Li、Yan Li、Indu Purushothaman、Susmita De、Bin Li、Hongping Zhu、Pattiyil Parameswaran、Qingsong Ye、Weiping Liu

  DOI：10.1021/om501288t

  日期：2015.9.14

  Reactions of the N-aryl(diphenylphospha:nyl)aminosilane Ph2PN(Ar)SiCl3-nMen (Ar = 2,4,6-Me3C6H2, n = 0 (la), 1 (2a), 2 (3a), 3 (4a); Ar = 2,6-iPr(2)C(6)H(3), n = 0 (lb), 1 (2b), 2 (3b), 3 (4b)) with methyl propiolate and dimethyl acetylenedicarboxylate (DMAD) give two types of products, the zwitterionic heterocycles [Ph2PN(2,4,6-Me3C6H2)SiCl3]-(HC=CCO2Me) (Sc) and [Ph2PN(Ar)SiCl3-nMen](MeO2CC=CCO2Me) (Ar = 2,4,6-Me3C6H2, n = 0 (5a), 1 (6a), 2 (7a); Ar = 2,6-iPr(2)C(6)H(3), n = 0 (5b), 1 (6b), 2 (7b)) and (Z)-silyliminophosphoranylalkene ArN=P(Ph-2)C(CO2Me)=C(CO2Me)SiMe3 (Ar = 2,4,6-Me3C6H2 (8a), 2,6-iPr(2)C(6)H(3) (8b)). The reaction of Ph2PN(SiMe3)(2) with DMAD gives only the acyclic alkene Me3SiN=P(Ph-2)(MeO2C)C=C(CO2Me)SiMe3 (9), which is similar to 8a,b. In these reactions, compounds 1a-4a and 1b-4b behave as N-geminal P/Si-based Lewis pairs, which undergo a dipolar cydoaddition reaction with the alkyne. The theoretical calculations indicate that the reactions proceed through a concerted cydoaddition reaction mechanism. The stability of these heterocycles decreases as the number of the Me substituent on the pentacoordinated Si atom increases. -When the Si center is substituted with three Me groups (4a,b), the heterocyclic intermediates undergo ring opening by Si-N bond cleavage and concomitant N=P bond formation resulting in 8a,b. The formation of the acyclic (Z)-alkene (8a,b and 9) can be considered as a stepwise S(N)2 reaction at the silicon center.
• NEILSON R. H.; WISIAN-NEILSON P.; WILBURN J. C., INORG. CHEM. 1980, 19, NO 2, 413-416
  作者：NEILSON R. H.、 WISIAN-NEILSON P.、 WILBURN J. C.

  DOI：——

  日期：——