[U(N(CH₂CH₂NSiPrⁱ₃)₃)(Cl)] | 1393903-60-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [U(N(CH₂CH₂NSiPrⁱ₃)₃)(Cl)]
• 英文别名: [U(Tren^TIPS)(Cl)]；U(N(CH₂CH₂NSiiPr₃)₃)(Cl)；Tris(triisopropylsilylamidoethyl)amine uranium(IV) chloride；2-[bis[2-tri(propan-2-yl)silylazanidylethyl]amino]ethyl-tri(propan-2-yl)silylazanide;uranium(4+);chloride
• CAS: 1393903-60-0
• 化学式: C₃₃H₇₅ClN₄Si₃U
• 分子量: 885.724
• InChiKey: KVQPNDRSLZRURP-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.94
• 重原子数：
  42
• 可旋转键数：
  21
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [U(N(CH₂CH₂NSiPrⁱ₃)₃)(Cl)] 以 四氢呋喃 、 甲苯 为溶剂， 反应 34.0h， 生成 [U(Tren^TIPS)((μ-N[H]K))2]
  参考文献：
  名称：

  Synthesis and Characterization of an f-Block Terminal Parent Imido [U═NH] Complex: A Masked Uranium(IV) Nitride

  摘要：

  Deprotonation of [U(Tren(TIPS))(NH2)] (1) [Tren(TIPS) = N(CH2CH2NSiPr3i)(3)] with organoalkali metal reagents MR (M = Li, R = Bu-t; M = Na-Cs, R = CH2C6H5) afforded the imido-bridged dimers [{U(Tren(TIPS)(mu-N[H]M)}(2)] [M = Li-Cs (2a-e)]. Treatment of 2c (M = K) with 2 equiv of 15-crown-S ether (15C5) afforded the uranium terminal parent imido complex [U(Tren(TIPS))(NH)][K(15C5)(2)] (3c), which can also be viewed as a masked uranium(IV) nitride. The uranium-imido linkage was found to be essentially linear, and theoretical calculations suggested sigma(2)pi(4) polarized U-N multiple bonding. Attempts to oxidize 3c to afford the neutral uranium terminal parent imido complex [U(Tren(TIPS))(NH)] (4) resulted in spontaneous disproportionation to give 1 and the uranium-nitride complex [U(Tren(TIPS))(N)] (5); this reaction is a new way to prepare the terminal uranium-nitride linkage and was calculated to be exothermic by -3.25 kcal mol(-1).

  DOI：

  10.1021/ja502405e
• 作为产物：
  描述：

  UCl₄(THF)₄ 、 以 四氢呋喃 为溶剂， 生成 [U(N(CH₂CH₂NSiPrⁱ₃)₃)(Cl)]
  参考文献：
  名称：

  5f轨道参与在三酰胺胺or（iv）和铀（iv）烷基的σ键易位反应趋势中的意外反转中的作用†

  摘要：

  我们报告了5f轨道参与在三酰胺胺th（IV）和铀（IV）烷基的σ键易位反应趋势中的意外反转中的作用。KCH 2 Ph与[U（Tren TIPS）（I）] [ 2a，Tren TIPS = N（CH 2 CH 2 NSiPr i 3）3 3-的反应]得到环金属盐[U {N（CH 2 CH 2 NSiPr i 3）2（CH 2 CH 2 NSiPr i 2 C [H] MeCH 2）}]（3a）的中间苄基配合物是不可观察到的。相反，当用KCH 2 Ph处理[Th（Tren TIPS）（I）]（2b）时，分离出[Th（Tren TIPS）（CH 2 Ph）]（4）。这是值得注意的，因为Tren N-甲硅烷基烷基金属烷基倾向于自发地环金属化。热解4个中cyclometallate的甲苯和形成的挤出结果[钍{N（CH 2 CH 2 NSiPr我3）2（CH 2 CH 2 NSiPr我2 C [H]机

  DOI：

  10.1039/c4sc00182f

文献信息

• Terminal Uranium(V/VI) Nitride Activation of Carbon Dioxide and Carbon Disulfide: Factors Governing Diverse and Well-Defined Cleavage and Redox Reactions
  作者：Peter A. Cleaves、Christos E. Kefalidis、Benedict M. Gardner、Floriana Tuna、Eric J. L. McInnes、William Lewis、Laurent Maron、Stephen T. Liddle

  DOI：10.1002/chem.201605620

  日期：2017.2.24

  as Ph3PS. Calculated reaction profiles reveal outer‐sphere reactivity for uranium(V) but inner‐sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE2 follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common

  提出了末端铀（V / VI）氮化物与CE 2（E = O，S）的反应性。观察到明确定义的C = E裂解，随后发生零电子，一电子和二电子氧化还原事件。氮化铀（V）[U（Tren TIPS）（N）] [K（B15C5）2 ]（1，Tren TIPS = N（CH 2 CH 2 NSi i Pr 3）3 ; B15C5 = benzo-15-crown- 5）与CO 2反应生成[U（Tren TIPS）（O）（NCO）] [K（B15C5）2 ]（3），而铀（VI）氮化物[U（Tren TIPS）（N）]（2）与CO 2反应给出可分离的[U（Tren TIPS）（O）（NCO）]（4）; 配合物4迅速分解为已知的[U（Tren TIPS）（O）]（5），并伴有拟议的N 2和CO形成，后者被捕集为钒钒加合物。与此相反，1种发生反应与CS 2，得到[U（特伦TIPS）（κ 2 -CS 3）] [K（B15C5）2
• Two-Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide
  作者：Peter A. Cleaves、David M. King、Christos E. Kefalidis、Laurent Maron、Floriana Tuna、Eric J. L. McInnes、Jonathan McMaster、William Lewis、Alexander J. Blake、Stephen T. Liddle

  DOI：10.1002/anie.201406203

  日期：2014.9.22

  Two‐electron reductive carbonylation of the uranium(VI) nitride [U(TrenTIPS)(N)] (2, TrenTIPS=N(CH2CH2NSiiPr3)3) with CO gave the uranium(IV) cyanate [U(TrenTIPS)(NCO)] (3). KC8 reduction of 3 resulted in cyanate dissociation to give [U(TrenTIPS)] (4) and KNCO, or cyanate retention in [U(TrenTIPS)(NCO)][K(B15C5)2] (5, B15C5=benzo‐15‐crown‐5 ether) with B15C5. Complexes 5 and 4 and KNCO were also prepared

  氮化铀(VI) [U(Tren TIPS )(N)] ( 2 , Tren TIPS =N(CH 2 CH 2 NSi i Pr 3 ) 3 ) 与CO的双电子还原羰基化得到氰酸铀(IV) [U（Tren TIPS）（NCO）]（3）。KC 8还原3导致氰酸盐解离，得到 [U(Tren TIPS )] ( 4 ) 和 KNCO，或氰酸盐保留在 [U(Tren TIPS )(NCO)][K(B15C5) 2 ] ( 5 , B15C5=苯并-15-冠-5醚）与B15C5。配合物5和4以及 KNCO 也分别由 CO 和氮化铀 (V) [U(Tren TIPS )(N)K} 2 ] ( 6 ) 制备，分别有或没有 B15C5。络合物5可以直接由 CO 和 [U(Tren TIPS )(N)][K(B15C5) 2 ] ( 7 )制备。值得注意的是，7与 CO 的反应速度比2快得多。这种前所未有的
• Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study
  作者：Jipan Yu、Kang Liu、Qunyan Wu、Bin Li、Xianghe Kong、Kongqiu Hu、Lei Mei、Liyong Yuan、Zhifang Chai、Weiqun Shi

  DOI：10.1002/cjoc.202100149

  日期：2021.8

  actinide complexes remains controversial to date. The introduction of 2-phosphaethynolate anion into actinide complexes is expected to investigate the reaction mode and the bonding property. Herein, we describe the functionalization of An(TrenTIPS)Cl (1: An = U; 2: An = Th) precursors with NaOCP(dioxane)2.5 through salt-elimination method leading to the formation of the corresponding uranium and thorium

  迄今为止，锕系化合物的共价问题仍然存在争议。将 2-磷酸乙炔根阴离子引入锕系配合物有望研究反应模式和键合性质。在本文中，我们描述了 An(Tren TIPS )Cl (1: An = U; 2: An = Th) 前体与 NaOCP(二恶烷) 2.5通过脱盐方法的功能化，导致形成相应的磷炔酸铀和钍物质: [U(Tren TIPS )(OCP)] (3) 和 [Th(Tren TIPS))(OCP)] (4)。这两种配合物通过核磁共振 (NMR)、FT-IR 光谱、UV-vis-NIR 光谱以及 X 射线晶体衍射进行了充分表征。两种配合物的计算分析表明，由于 U 的 5f 轨道贡献更多，U-O 键比 Th-O 键具有更多的共价键性质。
• Synthesis and Characterization of an f-Block Terminal Parent Imido [U═NH] Complex: A Masked Uranium(IV) Nitride
  作者：David M. King、Jonathan McMaster、Floriana Tuna、Eric J. L. McInnes、William Lewis、Alexander J. Blake、Stephen T. Liddle

  DOI：10.1021/ja502405e

  日期：2014.4.16

  Deprotonation of [U(Tren(TIPS))(NH2)] (1) [Tren(TIPS) = N(CH2CH2NSiPr3i)(3)] with organoalkali metal reagents MR (M = Li, R = Bu-t; M = Na-Cs, R = CH2C6H5) afforded the imido-bridged dimers [U(Tren(TIPS)(mu-N[H]M)}(2)] [M = Li-Cs (2a-e)]. Treatment of 2c (M = K) with 2 equiv of 15-crown-S ether (15C5) afforded the uranium terminal parent imido complex [U(Tren(TIPS))(NH)][K(15C5)(2)] (3c), which can also be viewed as a masked uranium(IV) nitride. The uranium-imido linkage was found to be essentially linear, and theoretical calculations suggested sigma(2)pi(4) polarized U-N multiple bonding. Attempts to oxidize 3c to afford the neutral uranium terminal parent imido complex [U(Tren(TIPS))(NH)] (4) resulted in spontaneous disproportionation to give 1 and the uranium-nitride complex [U(Tren(TIPS))(N)] (5); this reaction is a new way to prepare the terminal uranium-nitride linkage and was calculated to be exothermic by -3.25 kcal mol(-1).
• The role of 5f-orbital participation in unexpected inversion of the σ-bond metathesis reactivity trend of triamidoamine thorium(<scp>iv</scp>) and uranium(<scp>iv</scp>) alkyls
  作者：Benedict M. Gardner、Peter A. Cleaves、Christos E. Kefalidis、Jian Fang、Laurent Maron、William Lewis、Alexander J. Blake、Stephen T. Liddle

  DOI：10.1039/c4sc00182f

  日期：——

  thorium(IV) and uranium(IV) alkyls. Reaction of KCH2Ph with [U(TrenTIPS)(I)] [2a, TrenTIPS = N(CH2CH2NSiPri3)33−] gave the cyclometallate [UN(CH2CH2NSiPri3)2(CH2CH2NSiPri2C[H]MeCH2)}] (3a) with the intermediate benzyl complex not observable. In contrast, when [Th(TrenTIPS)(I)] (2b) was treated with KCH2Ph, [Th(TrenTIPS)(CH2Ph)] (4) was isolated; which is notable as Tren N-silylalkyl metal alkyls tend

  我们报告了5f轨道参与在三酰胺胺th（IV）和铀（IV）烷基的σ键易位反应趋势中的意外反转中的作用。KCH 2 Ph与[U（Tren TIPS）（I）] [ 2a，Tren TIPS = N（CH 2 CH 2 NSiPr i 3）3 3-的反应]得到环金属盐[U N（CH 2 CH 2 NSiPr i 3）2（CH 2 CH 2 NSiPr i 2 C [H] MeCH 2）}]（3a）的中间苄基配合物是不可观察到的。相反，当用KCH 2 Ph处理[Th（Tren TIPS）（I）]（2b）时，分离出[Th（Tren TIPS）（CH 2 Ph）]（4）。这是值得注意的，因为Tren N-甲硅烷基烷基金属烷基倾向于自发地环金属化。热解4个中cyclometallate的甲苯和形成的挤出结果[钍N（CH 2 CH 2 NSiPr我3）2（CH 2 CH 2 NSiPr我2 C [H]机