N-(2,4,6,2'',4'',6''-hexaisopropyl-[1,1':3',1'']terphenyl-5'-yl)-N',N'-bis[2-(2,4,6,2'',4'',6''-hexaisopropyl-[1,1':3',1'']terphenyl-5'-ylamino)ethyl]ethane-1,2-diamine | 443295-35-0

• 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-(2,4,6,2'',4'',6''-hexaisopropyl-[1,1':3',1'']terphenyl-5'-yl)-N',N'-bis[2-(2,4,6,2'',4'',6''-hexaisopropyl-[1,1':3',1'']terphenyl-5'-ylamino)ethyl]ethane-1,2-diamine
• 英文别名: tris(2-(2,4,6,2'',4'',6''-hexaisopropyl-1,1':3'1''-terphenyl-5'-amino)ethyl)amine；((3,5-(2,4,6-i-Pr3C6H2)2C6H3)NHCH2CH2)3N；(3,5-(2,4,6-i-Pr3C6H2)2C6H3NHCH2CH2)3N；(3,5-(2,4,6-i-Pr3C6H2)2C6H3NHC2H4)3N；H3[HIPTN3N]；N',N'-bis[2-[3,5-bis[2,4,6-tri(propan-2-yl)phenyl]anilino]ethyl]-N-[3,5-bis[2,4,6-tri(propan-2-yl)phenyl]phenyl]ethane-1,2-diamine
• CAS: 443295-35-0
• 化学式: C₁₁₄H₁₆₂N₄
• 分子量: 1588.57
• InChiKey: PCIUGAXCAWIXRS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  35.3
• 重原子数：
  118
• 可旋转键数：
  36
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  39.3
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(2,4,6,2'',4'',6''-hexaisopropyl-[1,1':3',1'']terphenyl-5'-yl)-N',N'-bis[2-(2,4,6,2'',4'',6''-hexaisopropyl-[1,1':3',1'']terphenyl-5'-ylamino)ethyl]ethane-1,2-diamine 、 tetrachlorobis(tetrahydrofurano)molybdenum(IV) 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以63%的产率得到[MoCl((3,5-(2,4,6-(isopropyl)3C6H2)2C6H3NCH2CH2)3N)]
  参考文献：
  名称：

  在三酰氨基钼络合物中保护良好的反应位点将二氮还原为氨

  摘要：

  我们合成了三酰氨基胺配体 ([(RNCH2CH2)3N]3-)，其中 R 是 3,5-(2,4,6-i-Pr3C6H2)2C6H3（六异丙基三联苯或 HIPT）。MoCl4(THF)2 和 H3[HIPTN3N] 在 THF 中反应，然后是 3.1 当量的 LiN(SiMe3)2，形成橙色的 [HIPTN3N]MoCl。[HIPTN3N]MoCl 在四氢呋喃中在氮气下用镁还原导致形成含有 {[HIPTN3N]Mo(N2)}- 离子的盐。{[HIPTN3N]Mo(N2)}- 离子可以被氯化锌氧化得到 [HIPTN3N]Mo(N2) 或质子化得到 [HIPTN3N]Mo-N=NH。已制备的其他相关化合物包括{[HIPTN3N]Mo-N=NH2}+、[HIPTN3N]MoN、{[HIPTN3N]Mo=NH}+和{[HIPTN3N]Mo(NH3)}+。（阴离子通常是 {B(3,5-(CF3)2C6H3)4}-

  DOI：

  10.1021/ja020186x
• 作为产物：
  描述：

  三(2-氨基乙基)胺 、 5'-bromo-2,4,6,2'',4'',6''-hexaisopropyl-1,1:3',1''-terphenyl 在 tris(dibenzylideneacetone)dipalladium (0) R-(+)-1,1'-联萘-2,2'-双二苯膦 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 20.0h， 以87%的产率得到N-(2,4,6,2'',4'',6''-hexaisopropyl-[1,1':3',1'']terphenyl-5'-yl)-N',N'-bis[2-(2,4,6,2'',4'',6''-hexaisopropyl-[1,1':3',1'']terphenyl-5'-ylamino)ethyl]ethane-1,2-diamine
  参考文献：
  名称：

  在三酰氨基钼络合物中保护良好的反应位点将二氮还原为氨

  摘要：

  我们合成了三酰氨基胺配体 ([(RNCH2CH2)3N]3-)，其中 R 是 3,5-(2,4,6-i-Pr3C6H2)2C6H3（六异丙基三联苯或 HIPT）。MoCl4(THF)2 和 H3[HIPTN3N] 在 THF 中反应，然后是 3.1 当量的 LiN(SiMe3)2，形成橙色的 [HIPTN3N]MoCl。[HIPTN3N]MoCl 在四氢呋喃中在氮气下用镁还原导致形成含有 {[HIPTN3N]Mo(N2)}- 离子的盐。{[HIPTN3N]Mo(N2)}- 离子可以被氯化锌氧化得到 [HIPTN3N]Mo(N2) 或质子化得到 [HIPTN3N]Mo-N=NH。已制备的其他相关化合物包括{[HIPTN3N]Mo-N=NH2}+、[HIPTN3N]MoN、{[HIPTN3N]Mo=NH}+和{[HIPTN3N]Mo(NH3)}+。（阴离子通常是 {B(3,5-(CF3)2C6H3)4}-

  DOI：

  10.1021/ja020186x

文献信息

• Synthesis of [(HIPTNCH₂CH₂)₃N]V Compounds (HIPT = 3,5-(2,4,6-<i>i</i>-Pr₃C₆H₂)₂C₆H₃) and an Evaluation of Vanadium for the Reduction of Dinitrogen to Ammonia
  作者：Nathan C. Smythe、Richard R. Schrock、Peter Müller、Walter W. Weare

  DOI：10.1021/ic061554r

  日期：2006.11.1

  Green [HIPTN3N]V(THF) ([HIPTN3N]3- = [(HIPTNCH2CH2)3N]3-, where HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3) can be prepared in a 70-80% yield via the addition of H3[HIPTN3N] to VCl3(THF)3 in THF, followed by the addition of LiN(SiMe3)2. From [HIPTN3N]V(THF), the following have been prepared: [HIPTN3N]VN2}K, [HIPTN3N]V(NH3), [HIPTN3N]V=NH, [HIPTN3N]V=NSiMe3, [HIPTN3N]V=O, [HIPTN3N]V=S, and [HIPTN3N]V(CO). No ammonia

  可以在70中制备绿色的[HIPTN3N] V（THF）（[HIPTN3N] 3- = [（HIPTNCH2CH2）3N] 3-，其中HIPT = 3,5-（2,4,6-i-Pr3C6H2）2C6H3）。通过向THF中的VCl 3（THF）3中添加H 3 [HIPTN 3 N]，然后添加LiN（SiMe 3）2，产率为-80％。由[HIPTN3N] V（THF），制备了以下物质：[HIPTN3N] VN2} K，[HIPTN3N] V（NH3），[HIPTN3N] V = NH，[HIPTN3N] V = NSiMe3，[HIPTN3N] V = O，[HIPTN3N] V = S，和[HIPTN3N] V（CO）。在相似的[HIPTN3N] Mo系统中成功使用的条件下，使用[HIPTN3N] VN2} K，[HIPTN3N] V = NH或[HIPTN3N] V（NH3）作为初始物质，
• Copper(I)‐Dioxygen Reactivity in a Sterically Demanding Tripodal Tetradentate tren Ligand: Formation and Reactivity of a Mononuclear Copper(II) End‐On Superoxo Complex
  作者：Yuki Kobayashi、Kei Ohkubo、Takashi Nomura、Minoru Kubo、Nobutaka Fujieda、Hideki Sugimoto、Shunichi Fukuzumi、Kei Goto、Takashi Ogura、Shinobu Itoh

  DOI：10.1002/ejic.201200177

  日期：2012.10

  Reaction of a copper(I) complex supported by a sterically demanding tripodal tetradentate ligand, HIPT3tren, and O2 gave a mononuclear copper(II) end-on superoxo complex. Spectroscopic (UV/Vis, resonance Raman, ESR, and 1H-NMR) and DFT studies have been performed. The O2-binding process as well as the reaction toward external substrates have been investigated kinetically to demonstrate the unique behavior

  由空间要求严格的三足四齿配体 HIPT3tren 和 O2 支撑的铜 (I) 络合物的反应得到单核铜 (II) 末端超氧络合物。已经进行了光谱（UV/Vis、共振拉曼、ESR 和 1H-NMR）和 DFT 研究。已经对 O2 结合过程以及对外部底物的反应进行了动力学研究，以证明铜 (II) 末端超氧复合物的独特行为，这可能是由于铜周围存在疏水核的结果由 HIPT3tren 配体创建的配位球。
• Synthesis of tungsten complexes that contain hexaisopropylterphenyl-substituted triamidoamine ligands, and reactions relevant to the reduction of dinitrogen to ammonia
  作者：Dmitry V Yandulov、Richard R Schrock

  DOI：10.1139/v05-013

  日期：2005.4.1

  [HIPTN₃N]WCl (WCl) can be synthesized readily by adding H₃[HIPTN₃N] to WCl₄(DME) followed by LiN(SiMe₃)₂ ([HIPTN₃N]^3– = [(HIPTNCH₂CH₂)₃N]^3– where HIPT = 3,5-(2,4,6-i-Pr₃C₆H₂)₂C₆H₃ = HexaIsoPropylTerphenyl). Reduction of WCl with KC₈ in benzene under N₂ yields WN=NK. WN=NK is readily oxidized in THF by ZnCl₂ to yield zinc metal and WN₂. Reduction of WN₂ to [WN₂]^– is reversible at –2.27 V vs. FeCp₂^+/0 in 0.1 mol/L [Bu₄N][BAr′₄]/PhF electrolyte (Ar′ = 3,5-(CF₃)₂C₆H₃), while oxidation of WN₂ to [WN₂]⁺ is also reversible at –0.66 V. Protonation of WN=NK by [Et₃NH][OTf] in benzene yields WN=NH essentially quantitatively. Protonation of WN=NH at N_β with [H(OEt)₂][BAr′₄] in ether affords [W=NNH₂][BAr′₄] quantitatively. Electrochemical reduction of [W=NNH₂][BAr′₄] in 0.1 mol/L [Bu₄N][BAr′₄]/PhF is irreversible at scan rates of up to 1 V/s. Addition of NaBAr′₄ and NH₃ to WCl in PhF yields [W(NH₃)][BAr′₄]. Electrochemical reduction of [W(NH₃)][BAr′₄] in 0.1 mol/L [Bu₄N][BAr′₄]/PhF is irreversible at –2.06 V vs. FeCp₂^+/0 at a scan rate of 0.5 V/s. Treatment of [W(NH₃)][BAr′₄] with triethylamine and [FeCp₂][PF₆] in C₆D₆, followed by LiN(SiMe₃)₂, yielded W≡N. Treatment of [W(NH₃)][BAr′₄] with LiBHEt₃ (1 mol/L in THF) results in formation of WH, which is converted to WH₃ upon exposure to an atmosphere of H₂. Attempts to prepare WN=NH by treating WN₂ with [2,6-LutH][BAr′₄] and CoCp₂ yielded only [W=NNH₂][BAr′₄]. [W=NNH₂][BAr′₄] is reduced to W=NNH₂ by CoCp^*₂, but this species disproportionates to yield WN=NH, W≡N, and ammonia. Reduction of [W(NH₃)][BAr′₄] with CoCp^*₂ does not yield any observable W(NH₃). Attempted catalytic reduction of dinitrogen using WN₂ as the catalyst under conditions identical or similar to those employed for catalytic reduction of dinitrogen by MoN₂ and related Mo complexes failed. Single crystal X-ray studies were carried out on W-N=NK, WN₂, W-N=NH, [W=NNH₂][BAr′₄], and [W(NH₃)][BAr′₄].Key words: dinitrogen, reduction, tungsten, ammonia.

  [HIPTN₃N]WCl（WCl）可以通过将H₃[HIPTN₃N]加入WCl₄(DME)中，然后加入LiN(SiMe₃)₂来轻松合成（[HIPTN₃N]^3– = [(HIPTNCH₂CH₂)₃N]^3–，其中HIPT = 3,5-(2,4,6-i-Pr₃C₆H₂)₂C₆H₃ = HexaIsoPropylTerphenyl）。在苯中，通过N₂下的KC₈还原WCl可以得到WN=NK。WN=NK在THF中通过ZnCl₂容易氧化为锌金属和WN₂。在0.1 mol/L [Bu₄N][BAr′₄]/PhF电解质中，WN₂的还原到[WN₂]^–在-2.27 V vs. FeCp₂^+/0下是可逆的，WN₂的氧化到[WN₂]⁺也在-0.66 V下是可逆的。WN=NK在苯中通过[Et₃NH][OTf]质子化可以基本定量地得到WN=NH。在醚中，通过[H(OEt)₂][BAr′₄]对WN=NH在N_β处质子化可以定量得到[W=NNH₂][BAr′₄]。在0.1 mol/L [Bu₄N][BAr′₄]/PhF中，[W=NNH₂][BAr′₄]的电化学还原在扫描速率高达1 V/s时是不可逆的。在PhF中，向WCl中加入NaBAr′₄和NH₃可以得到[W(NH₃)][BAr′₄]。在0.1 mol/L [Bu₄N][BAr′₄]/PhF中，[W(NH₃)][BAr′₄]的电化学还原在扫描速率为0.5 V/s时是不可逆的，在-2.06 V vs. FeCp₂^+/0处。在C₆D₆中，用三乙胺和[FeCp₂][PF₆]处理[W(NH₃)][BAr′₄]，然后加入LiN(SiMe₃)₂，可以得到W≡N。用LiBHEt₃（1 mol/L在THF中）处理[W(NH₃)][BAr′₄]可以得到WH，暴露在H₂气氛中可以转化为WH₃。尝试用[2,6-LutH][BAr′₄]和CoCp₂处理WN₂来制备WN=NH，但只得到[W=NNH₂][BAr′₄]。[W=NNH₂][BAr′₄]可以被CoCp^*₂还原为W=NNH₂，但这种物种会不均化产生WN=NH、W≡N和氨。用CoCp^*₂还原[W(NH₃)][BAr′₄]并不会产生任何可观察的W(NH₃)。尝试使用WN₂作为催化剂，在与MoN₂和相关Mo配合物催化还原二氮化物的条件相同或类似的条件下催化还原二氮化物失败。W-N=NK、WN₂、W-N=NH、[W=NNH₂][BAr′₄]和[W(NH₃)][BAr′₄]进行了单晶X射线研究。关键词：二氮化物、还原、钨、氨。
• Synthesis and Reactions of Molybdenum Triamidoamine Complexes Containing Hexaisopropylterphenyl Substituents
  作者：Dmitry V. Yandulov、Richard R. Schrock、Arnold L. Rheingold、Christopher Ceccarelli、William M. Davis

  DOI：10.1021/ic020505l

  日期：2003.2.1

  We have synthesized a triamidoamine ligand ([(RNCH2CH2)(3)N](3-)) in which R is 3,5-(2,4,6-i-Pr3C6H2)(2)C6H3 (hexaisopropylterphenyl or HIPT). The reaction between MOCl4(THF)(2) and H-3[HIPTN3N] in THF followed by 3.1 equiv of LiN(SiMe3)(2) led to formation of orange [HIPTN3N]MoCl. Reduction of MoCl (Mo = [HIPTN3N]Mo) with magnesium in THF under dinitrogen led to formation of salts that contain the Mo(N-2)}(-) ion. The Mo(N-2)}(-) ion can be oxidized by zinc chloride to give Mo(N-2) Or protonated to give MoN=NH. The latter was found to decompose to yield MoH. Other relevant compounds that have been prepared include Mo=N-NH2}(+) (by protonation of MoN=NH), Mo equivalent to N, Mo=NH}(+) (by protonation of Moequivalent toN), and Mo(NH3)}(+) (by treating MoCl with ammonia). (The anion is usually B(3,5-(CF3)(2)C6H3)(4)}(-) = BAr'(4)}(-).) X-ray studies were carried out on Mg(DME)(3)}(0.5)-[Mo(N-2)], MoN=NMgBr(THF)(3), Mo(N-2) Moequivalent toN, and Mo(NH3)}BAr'(4)}. These studies suggest that the HIPT substituent on the triamidoamine ligand creates a cavity that stabilizes a variety of complexes that might be encountered in a hypothetical Chatt-like dinitrogen reduction scheme, perhaps largely by protecting against bimolecular decomposition reactions.
• Synthesis of [(HIPTNCH₂CH₂)₃N]Cr Compounds (HIPT = 3,5-(2,4,6-<i>i</i>-Pr₃C₆H₂)₂C₆H₃) and an Evaluation of Chromium for the Reduction of Dinitrogen to Ammonia
  作者：Nathan C. Smythe、Richard R. Schrock、Peter Müller、Walter W. Weare

  DOI：10.1021/ic060549k

  日期：2006.9.1

  Red-black [HIPTN3N] Cr (1) ([HIPTN3N](3-) = [(HIPTNCH2CH2)(3)N](3-) where HIPT = 3,5-(2,4,6-i-Pr3C6H2)(2)C6H3) HexaIsoPropylTerphenyl) can be prepared from CrCl3, while green-black [HIPTN3N]Cr(THF) (2) can be prepared from CrCl3(THF)(3). Reduction of 1 vertical bar 2} ( which means either 1 or 2) with potassium graphite in ether at room temperature yields [HIPTN3N]CrK (3) as a yellow-orange powder. There is no evidence that dinitrogen is incorporated into 1, 2, or 3. Compounds that can be prepared readily from 1 vertical bar 2} include red [HIPTN3N] CrCO (4), blood-red [HIPTN3N] CrNO (6), and purple [HIPTN3N] CrCl ( 7, upon oxidation of 1 vertical bar 2} with AgCl). The dichroic (purple/green) Cr(VI) nitride, [HIPTN3N] CrN (8) was prepared from Bu4NN3 and 7. X-ray studies have been carried out on 4, 6, and 7, and on two co-crystallized compounds, 7 and [HIPTN3N] CrN3 ( 65: 35) and [HIPTN3N]CrN3 and 8 (50: 50). Exposure of a degassed solution of 1 vertical bar 2} to an atmosphere of ammonia does not yield "Cr(NH3)" as a stable and well-behaved species analogous to Mo(NH3). An attempt to reduce dinitrogen under conditions described for the catalytic reduction of dinitrogen by [HIPTN3N] Mo compounds with 8 yielded a substoichiometric amount (0.8 equiv) of ammonia, which suggests that some ammonia is formed from the nitride but none is formed from dinitrogen.