SP(NH(t)Bu)3 | 86148-15-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机硫代磷酸及其衍生物
• 英文名称: SP(NH(t)Bu)3
• 英文别名: Phosphorothioic triamide, N,N',N''-tris(1,1-dimethylethyl)-；N-bis(tert-butylamino)phosphinothioyl-2-methylpropan-2-amine
• CAS: 86148-15-4
• 化学式: C₁₂H₃₀N₃PS
• 分子量: 279.43
• InChiKey: UOAJSIIOPAZYHK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  68.2
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  三甲基铝 、 SP(NH(t)Bu)3 以 甲苯 为溶剂， 以82.8%的产率得到(Me2Al[(μ-S)(μ-N(t)Bu)P(NH(t)Bu)2])
  参考文献：
  名称：

  Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates:  EPR and DFT Investigations of the Persistent Neutral Radicals {Me₂Al[(μ-NR)(μ-N^tBu)P(μ-N^tBu)₂]Li(THF)₂}^• (R = SiMe₃, ^tBu)

  摘要：

  Reactions of (RNH)(3)PNSiMe3 (3a, R = Bu-t; 3b, R = Cy) with trimethylaluminum result in the formation of {Me-2-Al[(mu-(NBu)-Bu-t)(mu-NSiMe3)P((NHBu)-Bu-t)(2)]} (4) and the dimeric trisimidometaphosphate {Me2Al[(mu-NCy)(mu-NSiMe3)P(mu-NCy)(2)P-(mu-NCy)(mu-NSiMe3)]AIMe(2)} (5a), respectively. The reaction of SP((NHBu)-Bu-t)(3) (2a) with 1 or 2 equiv of AIMe(3) yields {Me2Al[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)]} (7) and {Me2Al[(mu-S)(mu-(NBu)-Bu-t)P(mu-(NHBu)-Bu-t)(mu-(NBu)-Bu-t)]AlMe2} (8), respectively. Metalation of 4 with (BuLi)-Bu-n produces the heterobimetallic species {Me2Al[(mu-(NBu)-Bu-t)(mu-NSiMe3)P(mu-(NHBu)-Bu-t)(mu-(NBu)-Bu-t)]-Li(THF)(2)} (9a) and {[Me2Al][Li](2)[P((NBu)-Bu-t)(3)(NSiMe3)]} (10) sequentially; in THF solutions, solvation of 10 yields an ion pair containing a spirocyclic tetraimidophosphate monoanion, Similarly, the reaction of ((BuNH)-Bu-t)(3)(PNBu)-Bu-t with AIMe(3) followed by 2 equiv of (BuLi)-Bu-n generates {Me2Al[(mu-(NBu)-Bu-t)(2)(mu(2)-(NBu)-Bu-t)(2)(mu(2)-THF)[Li(THF)](2)} (11a), Stoichiometric oxidations of 10 and 11a with iodine yield the neutral spirocyclic radicals {Me2Al[(mu-NR)(mu-(NBu)-Bu-t)P(mu-(NBu)-Bu-t)(2)]Li-(THF)(2)}(center dot) (13a, R = SiMe3; 14a, R = Bu-t), which have been characterized by electron paramagnetic resonance spectroscopy. Density functional theory calculations confirm the retention of the spirocyclic structure and indicate that the spin density in these radicals is concentrated on the nitrogen atoms of the PN2Li ring, When 3a or 3b is treated with 0.5 equiv of dibutylmagnesium, the complexes {Mg[(mu-(NBu)-Bu-t)(mu-(NHBu)-Bu-t)P((NHBu)-Bu-t)(NSiMe3)](2)} (15) and {Mg[(mu-NCy)(mu-NSiMe3)P(NHCy)(2)](2)} (16) are obtained, respectively. The addition of 0.5 equiv of MgBu2 to 2a results in the formation of {Mg[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)](2)} (17), which produces the hexameric species {[MgOH]-[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)]}(6) (18) upon hydrolysis. Compounds 4, 5a, 7-11a, and 15-17 have been characterized by multinuclear (H-1, C-13, and P-31) NMR spectroscopy and, in the case of 5a, 9a center dot 2THF, 11a, and 18, by X-ray crystallography.

  DOI：

  10.1021/ic050689e
• 作为产物：
  描述：

  叔丁胺 在 三氯硫磷 作用下， 以 乙腈 为溶剂， 生成 1,3,N,N'-Tetra-tert-butyl-2,4-dithioxo-2λ⁵,4λ⁵-[1,3,2,4]diazadiphosphetidine-2,4-diamine 、 SP(NH(t)Bu)3
  参考文献：
  名称：

  Hursthouse, Michael B.; Ibrahim, Ezzeldine H.; Parkes, Harold G., Phosphorus and Sulfur and the Related Elements, 1986, vol. 28, p. 261 - 266

  摘要：

  DOI：

文献信息

• Steric effects on the mode of aggregation and reactivity of clusters formed from the lithiation of trisamidothiophosphates
  作者：Tristram Chivers、Mark Krahn、Masood Parvez、Gabriele Schatte

  DOI：10.1039/b105360b

  日期：——

  Lithiation of SP[N(H)R]3 with LiBun produces the dimers [(THF)LiSP(NR)(NHR)2]2 (R = Pri) or [LiSP(NR)- (NHR)2][(THF)LiSP(NR)2(NHR)]}2 (R = But) with central Li2N2 or Li2S2 rings, respectively; further lithiation yields the dianion [SP(NR)2(NHR)]2− (R = Pri) or leads to sulfur extrusion when R = But.

  用 LiBun 锂化 SP[N(H)R]3 会产生二聚体[(THF)LiSP(NR)(NHR)2]2（R = Pri）或[LiSP(NR)- (NHR)2][(THF)LiSP(NR)2(NHR)]}2 （R = But），其中心环分别为 Li2N2 或 Li2S2；进一步锂化产生二元离子 [SP(NR)2(NHR)]2-（R = Pri），或者当 R = But 时导致硫挤出。
• Synthesis and structural characterization of zinc complexes of the imido–amido phosphate anions OP[(NHR)_3–<i>_x</i>(NR)]<i>^x</i>^– (R = Me, <i>t</i>-Bu; <i>x</i> = 1–3) and EP[(NH-<i>t</i>-Bu)₂(N-<i>t</i>-Bu)]^– (E = S, NSiMe₃)
  作者：Andrea F Armstrong、Tristram Chivers、Mark Krahn、Masood Parvez

  DOI：10.1139/v05-183

  日期：2005.10.1

  The reaction of OP(NH-t-Bu)₃ with 1 equiv. of ZnMe₂ generates the dimeric eight-membered ring MeZn[(µ-NH-t-Bu)(µ-N-t-Bu)P(NH-t-Bu)(µ-O)]}₂ (5) and the cubane [MeZn]₃[OP(N-t-Bu)₃][OP(NH-t-Bu)₃]} (6), which contains the first known trisimidophosphate trianion. A related complex Zn[ZnMe]₂[OP(N-t-Bu)(NH-t-Bu)₂][OP(N-t-Bu)₃]} (7) is obtained by the reaction of OP(NH-t-Bu)₃ with ZnMe₂ in a 2:3 molar ratio. The treatment of OP(NHMe)₃ with 1 equiv. of ZnMe₂ produces the oxide-templated cluster Zn₄(µ₄-O)[OP(NMe)(NHMe)₂]₄[OP(NMe)₂(NHMe)]}₂ (8). Each half of this centrosymmetric dimer contains a tetrahedral arrangement of four 4-coordinate Zn²⁺ ions surrounding the central µ₄-O^2- anion. The reaction of SP(NH-t-Bu)₃ with ZnMe₂ in a 1:1 molar ratio generates the dimer MeZn(µ-S)(µ-N-t-Bu)P(NH-t-Bu)₂}₂ (10), which has a ladder-type structure. When a 2:1 molar ratio of the same reagents is employed, the bis(N,S)-chelated complex Zn[(µ-S)(µ-N-t-Bu)P(NH-t-Bu)₂]₂} (11) is obtained. The monomeric N,N′-chelated complex MeZn[(µ-N-t-Bu)(µ-NSiMe₃)P(NH-t-Bu)₂]} (12) results from the reaction of Me₃SiNP(NH-t-Bu)₃ with 1 equiv. of dimethylzinc. All new compounds have been characterized by multinuclear (¹H, ¹³C, and ³¹P) NMR spectroscopy and, in the case of 5, 6, 7, 8, and 10, by X-ray structural determinations.Key words: zinc, phosphate, imido ligands, sulfur.

  OP(NH-t-Bu)₃与1当量的ZnMe₂反应生成二聚体八元环MeZn[(µ-NH-t-Bu)(µ-N-t-Bu)P(NH-t-Bu)(µ-O)]}₂（5）和方盒[MeZn]₃[OP(N-t-Bu)₃][OP(NH-t-Bu)₃]}（6），其中包含已知的第一个三咪唑磷酸根离子。通过OP（NH-t-Bu）₃与ZnMe₂在2:3的摩尔比下反应得到相关的配合物Zn[ZnMe]₂[OP(N-t-Bu)(NH-t-Bu)₂][OP(N-t-Bu)₃]}（7）。OP（NHMe）₃与1当量的ZnMe₂反应产生氧化物模板的簇Zn₄(µ₄-O)[OP(NMe)(NHMe)₂]₄[OP(NMe)₂(NHMe)]}₂（8）。这个中心对称二聚体的每一半都包含四个4配位的Zn²⁺离子围绕中心的µ₄-O^2-离子的四面体排列。SP（NH-t-Bu）₃与ZnMe₂在1:1的摩尔比下反应生成梯形结构的二聚体MeZn(µ-S)(µ-N-t-Bu)P(NH-t-Bu)₂}₂（10）。当使用相同试剂的2:1摩尔比时，会得到双（N，S）螯合的配合物Zn[(µ-S)(µ-N-t-Bu)P(NH-t-Bu)₂]₂}（11）。单核的N，N′-螯合配合物MeZn[(µ-N-t-Bu)(µ-NSiMe₃)P(NH-t-Bu)₂]}（12）是由Me₃SiNP（NH-t-Bu）₃与1当量的二甲基锌反应得到的。所有新化合物都通过多核（¹H，¹³C和³¹P）NMR光谱和5、6、7、8和10的X射线结构测定进行了表征。关键词：锌，磷酸盐，亚胺配体，硫。
• Hursthouse, Michael B.; Ibrahim, Ezzeldine H.; Parkes, Harold G., Phosphorus and Sulfur and the Related Elements, 1986, vol. 28, p. 261 - 266
  作者：Hursthouse, Michael B.、Ibrahim, Ezzeldine H.、Parkes, Harold G.、Shaw, Leyla S.、Shaw, Robert A.、Watkins, David A.

  DOI：——

  日期：——
• Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates:  EPR and DFT Investigations of the Persistent Neutral Radicals {Me₂Al[(μ-NR)(μ-N<i>^t</i>Bu)P(μ-N<i>^t</i>Bu)₂]Li(THF)₂}^• (R = SiMe₃, <i>^t</i>Bu)
  作者：Andrea Armstrong、Tristram Chivers、Heikki M. Tuononen、Masood Parvez

  DOI：10.1021/ic050689e

  日期：2005.8.1

  Reactions of (RNH)(3)PNSiMe3 (3a, R = Bu-t; 3b, R = Cy) with trimethylaluminum result in the formation of Me-2-Al[(mu-(NBu)-Bu-t)(mu-NSiMe3)P((NHBu)-Bu-t)(2)]} (4) and the dimeric trisimidometaphosphate Me2Al[(mu-NCy)(mu-NSiMe3)P(mu-NCy)(2)P-(mu-NCy)(mu-NSiMe3)]AIMe(2)} (5a), respectively. The reaction of SP((NHBu)-Bu-t)(3) (2a) with 1 or 2 equiv of AIMe(3) yields Me2Al[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)]} (7) and Me2Al[(mu-S)(mu-(NBu)-Bu-t)P(mu-(NHBu)-Bu-t)(mu-(NBu)-Bu-t)]AlMe2} (8), respectively. Metalation of 4 with (BuLi)-Bu-n produces the heterobimetallic species Me2Al[(mu-(NBu)-Bu-t)(mu-NSiMe3)P(mu-(NHBu)-Bu-t)(mu-(NBu)-Bu-t)]-Li(THF)(2)} (9a) and [Me2Al][Li](2)[P((NBu)-Bu-t)(3)(NSiMe3)]} (10) sequentially; in THF solutions, solvation of 10 yields an ion pair containing a spirocyclic tetraimidophosphate monoanion, Similarly, the reaction of ((BuNH)-Bu-t)(3)(PNBu)-Bu-t with AIMe(3) followed by 2 equiv of (BuLi)-Bu-n generates Me2Al[(mu-(NBu)-Bu-t)(2)(mu(2)-(NBu)-Bu-t)(2)(mu(2)-THF)[Li(THF)](2)} (11a), Stoichiometric oxidations of 10 and 11a with iodine yield the neutral spirocyclic radicals Me2Al[(mu-NR)(mu-(NBu)-Bu-t)P(mu-(NBu)-Bu-t)(2)]Li-(THF)(2)}(center dot) (13a, R = SiMe3; 14a, R = Bu-t), which have been characterized by electron paramagnetic resonance spectroscopy. Density functional theory calculations confirm the retention of the spirocyclic structure and indicate that the spin density in these radicals is concentrated on the nitrogen atoms of the PN2Li ring, When 3a or 3b is treated with 0.5 equiv of dibutylmagnesium, the complexes Mg[(mu-(NBu)-Bu-t)(mu-(NHBu)-Bu-t)P((NHBu)-Bu-t)(NSiMe3)](2)} (15) and Mg[(mu-NCy)(mu-NSiMe3)P(NHCy)(2)](2)} (16) are obtained, respectively. The addition of 0.5 equiv of MgBu2 to 2a results in the formation of Mg[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)](2)} (17), which produces the hexameric species [MgOH]-[(mu-S)(mu-(NBu)-Bu-t)P((NHBu)-Bu-t)(2)]}(6) (18) upon hydrolysis. Compounds 4, 5a, 7-11a, and 15-17 have been characterized by multinuclear (H-1, C-13, and P-31) NMR spectroscopy and, in the case of 5a, 9a center dot 2THF, 11a, and 18, by X-ray crystallography.