tris(hexamethyldisilylamido)chlorocerium(VI) | 373385-32-1

• 英文名称: tris(hexamethyldisilylamido)chlorocerium(VI)
• 英文别名: Ce[N(SiMe3)2]3Cl；CeCl[N(SiMe₃)₂]₃；[cerium(IV)(bis(trimethylsilyl)amide)3(chloride)]；CeCl[N(SiMe3)2]3
• CAS: 373385-32-1
• 化学式: C₁₈H₅₄CeClN₃Si₆
• 分子量: 656.733
• InChiKey: ITBKHINGGQZYQG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  tris(hexamethyldisilylamido)chlorocerium(VI) 、 sodium thiocyanide 以 四氢呋喃 为溶剂， 以40%的产率得到Ce(NCS)[N(SiMe₃)₂]₃
  参考文献：
  名称：

  Synthesis and Analysis of a Family of Cerium(IV) Halide and Pseudohalide Compounds

  摘要：

  The first complete series of isostructural cerium(IV) halide complexes in a conserved ligand framework was isolated by halogen-exchange reactions of CeF[N(SiMe3)(2)](3) with Me3SiX (X = Cl-, Br-, I-). The use of Me3SiX reagents represents a useful method for obtaining cerium(IV) complexes. Spectroscopic, electrochemical, and computational analyses were used to describe the effects of halide coordination on the cerium(IV) metal center. Cerium(IV) complexes of the pseudohalide ligands: N-3(-) and NCS- were also synthesized and evaluated in comparison to the halide congeners. The results showed that the complexes exhibited reduction potentials and electronic absorption energies that varied with the identity of the halide or pseudohalide ligand.

  DOI：

  10.1021/ic500969r
• 作为产物：
  描述：

  tris(bis(trimethylsilylamido))cerium(III) 以 四氢呋喃 、 正己烷 为溶剂， 反应 16.0h， 生成 tris(hexamethyldisilylamido)chlorocerium(VI)
  参考文献：
  名称：

  Synthesis, Bonding, and Reactivity of a Cerium(IV) Fluoride Complex

  摘要：

  Oxidation of Ce[N(SiMe3)(2)](3) in the presence of PF6- or BF4- afforded isolation of CeF[N(SiMe3)(2)](3). Structural and electrochemical characterization shows that this compound is in its tetravalent oxidation state and contains a terminal fluoride ligand. Spectroscopy and density functional theory have been used to characterize the Ce-F bond as ionic, which is reinforced by an initial reactivity study that demonstrates the nucleophilicity of the fluoride ligand.

  DOI：

  10.1021/ic402769u

文献信息

• Exploration of the Solid- and Solution-State Structures and Electrochemical Properties of Ce^IV(atrane) Complexes
  作者：Lukman A. Solola、Thibault Cheisson、Qiaomu Yang、Patrick J. Carroll、Eric J. Schelter

  DOI：10.1021/acs.inorgchem.8b00712

  日期：2018.9.4

  Chemical oxidation of cerium complexes can be unpredictable because of labile metal–ligand bonds leading to ligand redistribution. The use of tripodal frameworks such as silyl-substituted tren ligands (NN′3 = [N(CH2CH2N(SiMe2tBu))3]3–) and a tris(hydroxylaminato) ligand, [((2-tBuNO)C6H4CH2)3N]3– (TriNOx3–), has been shown to mitigate ligand redistribution effects to allow access to tetravalent cerium

  铈配合物的化学氧化可能是不可预测的，因为不稳定的金属-配体键会导致配体重新分布。（NN'使用三足框架，例如甲硅烷基取代TREN配体3 = [N（CH 2 CH 2 N（森达2吨丁基））3 ] 3-）和三（hydroxylaminato）配体，[（（2- t BuNO）C 6 H 4 CH 2）3 N] 3–（TriNOx 3–）已经显示出减轻配体重新分布的作用，从而允许获得具有不同顶端配体的四价铈配合物。在当前的工作中，研究了Ce IV与相关的三脚架atrane 3–（H 3 atrane = [N（CH 2 C（CH 3）2 OH）3 ]）配体骨架的配位化学。合成了一系列具有辅助氯化物，甲硅烷基酰胺和芳基氧化物配体的Ce IV（阿曲汀）配合物，并通过X射线晶体学对其进行了表征。使用1 H和扩散有序（DOSY）NMR光谱学研究了这些络合物的溶液状态行为。Ce的电化学稳定检查了atrane
• Oxidation in Nonclassical Organolanthanide Chemistry:  Synthesis, Characterization, and X-ray Crystal Structures of Cerium(III) and -(IV) Amides
  作者：Peter B. Hitchcock、Alexander G. Hulkes、Michael F. Lappert

  DOI：10.1021/ic035100v

  日期：2004.2.1

  [Ce(NR(2))(3)] (R = SiMe(3)) with TeCl(4) in tetrahydrofuran solution gave a mixture of two major products in a combined yield of ca. 50% based on available metal: (i) the Ce(IV) amide [CeCl(NR(2))(3)] (1), which was isolated as purple needles and identified on the basis of (1)H NMR and mass spectra, microanalysis, and a single-crystal X-ray analysis [C(18)H(54)CeClN(3)Si(6), rhombohedral, R3c (No

  [Ce（NR（2））（3）]（R = SiMe（3））与TeCl（4）在四氢呋喃溶液中的混合物给出了两种主要产物的混合物，总收率约为0.23。基于可用金属的50％：（i）铈（IV）酰胺[CeCl（NR（2））（3）]（1），被分离为紫色针状物，并根据（1）H NMR和质谱，显微分析和单晶X射线分析[C（18）H（54）CeClN（3）Si（6），菱面体，R3c（编号161），a = b = 18.4508（7）A ，c = 16.8934（7）A，Z = 6]；（ii）不稳定的[[Ce（NR（2））（2）（mu-Cl）（thf）]（2）]（2），为无色嵌段[C（32）H（88）Ce（2）Cl （2）N（4）O（2）Si（8），单斜晶系，P2（1）/ n（14号），a = 14.506（3）A，b = 13.065（3）A，c = 16.779（ 3）A，β= 113.789（12）度，Z =
• Luminescent Ce(III) Complexes as Stoichiometric and Catalytic Photoreductants for Halogen Atom Abstraction Reactions
  作者：Haolin Yin、Patrick J. Carroll、Jessica M. Anna、Eric J. Schelter

  DOI：10.1021/jacs.5b05411

  日期：2015.7.29

  their (2)A1 excited states afforded photochemical halogen atom abstraction reactions from sp(3) and sp(2) C-X (X = Cl, Br, I) bonds for the first time with a lanthanide cation. The dehalogenation reactions could be turned over with catalytic amounts of photosensitizers by coupling salt metathesis and reduction to the photopromoted atom abstraction reactions.

  发光 Ce(III) 配合物，Ce[N(SiMe3)2]3 (1) 和 [(Me3Si)2NC(RN)2]Ce[N(SiMe3)2]2 (R = (i)Pr, 1-( i)Pr；R = Cy, 1-Cy)，C(3v) 和 C(2v) 解对称性显示可见光区域中的吸收 4f → 5d 电子跃迁。在 553、518 和 523 nm 处观察到 1、1-(i)Pr 和 1-Cy 的发射带，其寿命分别为 24、67 和 61 ns。对 1 和 1-(i)Pr 的瞬态密度泛函理论 (TD-DFT) 研究揭示了 (2)A1 激发态对应于单独占据的 5d(z(2)) 轨道。1、1-(i)Pr 和 1-Cy 在其 (2)A1 激发态的强还原金属基特征提供了 sp(3) 和 sp(2) CX (X = Cl, Br) 的光化学卤原子提取反应, I) 第一次与镧系阳离子键合。
• Cerium Photosensitizers: Structure–Function Relationships and Applications in Photocatalytic Aryl Coupling Reactions
  作者：Haolin Yin、Patrick J. Carroll、Brian C. Manor、Jessica M. Anna、Eric J. Schelter

  DOI：10.1021/jacs.6b02248

  日期：2016.5.11

  complexes with the general formulas [(Me3Si)2NC(N(i)Pr)2]xCe(III)[N(SiMe3)2]3-x (x = 0, 1-N; x = 1, 2-N, x = 2, 3-N; x = 3, 4) and [(Me3Si)2NC(N(i)Pr)2]xCe(III)(OAr)3-x (x = 0, 1-OAr; x = 1, 2-OAr, x = 2, 3-OAr; x = 3, 4) were developed, featuring photoluminescence quantum yields up to 0.81(2) and lifetimes to 117(1) ns. Although the 4f → 5d absorptive transitions for these complexes were all found at ca

  具有通式 [(Me3Si)2NC(N(i)Pr)2]xCe(III)[N(SiMe3)2]3-x (x = 0, 1-N; x = 1, 2-N, x = 2, 3-N; x = 3, 4) 和 [(Me3Si)2NC(N(i)Pr)2]xCe(III)(OAr)3-开发了 x (x = 0, 1-OAr; x = 1, 2-OAr, x = 2, 3-OAr; x = 3, 4)，其光致发光量子产率高达 0.81(2)，寿命高达 117( 1) ns。尽管这些复合物的 4f → 5d 吸收跃迁都在约 420 nm，它们的发射带表现出很大的斯托克斯位移，最大值出现在 1-N 的 553 nm、2-N 的 518 nm、3-N 的 508 nm 和 459 nm 的 4，具有黄色、柠檬绿、绿色、和蓝光，分别。结合瞬态密度泛函理论 (TD-DFT) 计算和光谱研究表明，这些配合物的长寿命 (2)D
• Cerium(<scp>iv</scp>) complexes with guanidinate ligands: intense colors and anomalous electronic structures
  作者：Yusen Qiao、Haolin Yin、Liane M. Moreau、Rulin Feng、Robert F. Higgins、Brian C. Manor、Patrick J. Carroll、Corwin H. Booth、Jochen Autschbach、Eric J. Schelter

  DOI：10.1039/d0sc05193d

  日期：——

  A series of cerium(IV) mixed-ligand guanidinate–amide complexes, [(Me3Si)2NC(NiPr)2]xCeIV[N(SiMe3)2]3−x}+ (x = 0–3), was prepared by chemical oxidation of the corresponding cerium(III) complexes, where x = 1 and 2 represent novel complexes. The Ce(IV) complexes exhibited a range of intense colors, including red, black, cyan, and green. Notably, increasing the number of the guanidinate ligands from

  一系列铈( IV )混合配体胍盐-酰胺络合物，[(Me 3 Si) 2 NC(N i Pr) 2 ] x Ce IV [N(SiMe 3 ) 2 ] 3− x } + ( x = 0-3），是通过化学氧化相应的铈（III）配合物制备的，其中x = 1和2代表新型配合物。Ce( IV）复合物表现出一系列强烈的颜色，包括红色、黑色、青色和绿色。值得注意的是，将胍基配体的数量从零增加到三个会导致 THF 中吸收带从 503 nm (2.48 eV) 显着红移到 785 nm (1.58 eV)。X射线吸收近边结构（XANES）光谱表明，更多的胍配体增加了f占有率（n f ），并揭示了所有Ce（ IV ）配合物的多构型基态。循环伏安实验表明，更多的胍配体对 Ce( IV ) 氧化态的稳定性较差。此外，Ce( IV）三（胍）配合物表现出与温度无关的顺磁性（TIP），这是由于具有相当大磁矩的基态和激