magnesocene

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: magnesocene
• 英文别名: bis-(cyclopentadienyl) magnesium；bis(cyclopentadienyl) magnesium；bis cyclopentadienyl magnesium；bis(cyclopentadienyl)magnesium；bis-cyclopentadienyl-magnesium；bis-cyclopentadienylmagnesium
• 化学式: 2C₅H₅*Mg
• 分子量: 154.494
• InChiKey: NPJMMORYSGFCLJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.02
• 重原子数：
  6.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  magnesocene 在 potassium biphenyl or potassium phenanthrene 作用下， 以 乙二醇二甲醚 为溶剂， 生成 magnesium
  参考文献：
  名称：

  Size-Dependent Hydrogen Storage Properties of Mg Nanocrystals Prepared from Solution

  摘要：

  Mg nanocrystals of controllable sizes were prepared in gram quantities by chemical reduction of magnesocene using a reducing solution of potassium with an aromatic hydrocarbon (either biphenyl, phenanthrene, or naphthalene). The hydrogen sorption kinetics were shown to be dramatically faster for nanocrystals with smaller diameters, although the activation energies calculated for hydrogen absorption (115-122 kJ/mol) and desorption (126-160 kJ/mol) were within previously measured values for bulk Mg. This large rate enhancement cannot be explained by the decrease in particle size alone but is likely due to an increase in the defect density present in smaller nanocrystals.

  DOI：

  10.1021/ja201791y

文献信息

• Niobium η-cyclopentadienyl compounds with imido and amido ligands derived from tert-butylamine
  作者：Martin J. Humphries、Malcolm L. H. Green、Michael A. Leech、Vernon C. Gibson、Matthew Jolly、David N. Williams、Mark R. J. Elsegood、William Clegg

  DOI：10.1039/b006333i

  日期：——

  The niobium η-cyclopentadienyl compounds with imido and amido ligands [Nb(η-C5H5)(NtBu)(NHtBu)Cl] 1,* [Nb(η-C5H5)(NtBu)(NHtBu)nBu] 2, [Nb(η-C5H5)(NtBu)(NHtBu)2] 3, [Nb(η-C5H5)(NtBu)(NHtBu)Me] 4, [Nb(η-C5H5)(η1-C5H5)(NtBu)(NHtBu)] 5, [Nb(η-C5H4)CMe2(η1-C5H4)}(NtBu)(NHtBu)] 6, [Nb(η-C5H5)N(C6H3iPr2-2,6)}(NHtBu)Cl] 7,* [Nb(η-C5H5)N(C6H3iPr2-2,6)}(NHtBu)Me] 8, [Nb(η-C5H5)(NtBu)(NEt2)Cl] 9 and [Nb(η-C5H5)(NtBu)(NHtBu)(NEt2)] 10 have been prepared (* indicates the crystal structure has been determined). A correlation between the chemical shift of the NH proton and the value of Δδ measured between the α and β carbons of the tert-butyl groups of the amido ligands is discussed in relation to the degree of electron donation from the amido ligand to the niobium centre.

  铌η-环戊二烯化合物与亚胺和氨基配体[Nb(η-C5H5)(NtBu)(NHtBu)Cl] 1,* [Nb(η-C5H5)(NtBu)(NHtBu)nBu] 2, [Nb(η-C5H5)(NtBu)(NHtBu)2] 3, [Nb(η-C5H5)(NtBu)(NHtBu)Me] 4, [Nb(η-C5H5)(η1-C5H5)(NtBu)(NHtBu)] 5, [Nb(η-C5H4)CMe2(η1-C5H4)}(NtBu)(NHtBu)] 6, [Nb(η-C5H5)N(C6H3iPr2-2,6)}(NHtBu)Cl] 7,* [Nb(η-C5H5)N(C6H3iPr2-2,6)}(NHtBu)Me] 8, [Nb(η-C5H5)(NtBu)(NEt2)Cl] 9 和 [Nb(η-C5H5)(NtBu)(NHtBu)(NEt2)] 10 已被制备（*表示晶体结构已确定）。关于氨基配体向铌中心提供电子的程度，讨论了氨基配体叔丁基的α和β碳之间测得的Δδ值与NH质子的化学位移之间的相关性。
• Niobium- and tantalum-benzamidinato complexes with trimethylphosphine, imido, or η-cyclopentadienyl derivatives
  作者：Chi-Tien Chen、Linda H. Doerrer、V. Cliff Williams、Malcolm L. H. Green

  DOI：10.1039/a909333h

  日期：——

  The mononuclear benzamidinato compounds, [M(2,4,6-tri-iPr)C6H2C(NSiMe3)2}Cl4] (M = Nb (1) or Ta (2*)), [Nb(2,4,6-tri-iPr)C6H2C(NSiMe3)2}Cl4(PMe3)] (4*), [M(2,4,6-tri-iPr)C6H2C(NSiMe3)2}(NtBu)(H2NtBu)Cl2] (M = Nb (5), M = Ta (6)), [Nb(2,4,6-tri-iPr)C6H2C(NSiMe3)2}(NtBu)(L)Cl2] (L = THF (7), L = pyridine (8)), and [M(2,4,6-tri-iPr)C6H2C(NSiMe3)2}(η-C5H5)Cl3] (M = Nb (9), M = Ta (10*), and a nitrile tantalum complex, [Ta(2,4,6-tri-iPr)C6H2CN}Cl5] (3*), obtained in a side-reaction have been prepared:* indicates the crystal structures have been determined. Variable temperature NMR studies show there is hindered rotation of the aryl group around Cipso–C bonds for compounds 5 and 6; ΔG‡ = 55.2 kJ mol−1 at 268 K for 5. Hindered rotation about the N–Si bonds for compounds 9 and 10 occurs with the ΔG‡ = 51.0 kJ mol−1 at 273 K and 40.6 kJ mol−1 at 213 K for 10. The compounds 1, 5 and 9 are very poor pre-catalysts for ethene polymerisation.

  单核苯甲酰胺化合物,[M(2,4,6-三-iPr)C6H2C(NSiMe3)2}Cl4](M=Nb(1)或Ta(2*)),[Nb(2,4,6-三-iPr)C6H2C(NSiMe3)2}Cl4(PMe3)](4*),[M(2,4,6-三-iPr)C6H2C(NSiMe3)2}(NtBu)(H2NtBu)Cl2](M=Nb(5),M=Ta(6)),[Nb(2,4,6-三-iPr)C6H2C(NSiMe3)2}(NtBu)(L)Cl2](L=THF(7),L=吡啶(8)),和[M(2,4,6-三-iPr)C6H2C(NSiMe3)2}(η-C5H5)Cl3](M=Nb(9),M=Ta(10*)),以及一个腈钽配合物,[Ta(2,4,6-三-iPr)C6H2CN}Cl5](3*),在副反应中获得,已制备完成:*表示晶体结构已确定。变温核磁共振研究表明,对于化合物5和6,芳基绕Cipso-C键的旋转受阻;在268 K时,ΔG‡=55.2 kJ mol-1(5)。化合物9和10的N-Si键旋转受阻,ΔG‡在273 K时为51.0 kJ mol-1,在213 K时为40.6 kJ mol-1(10)。化合物1、5和9是乙烯聚合的极差预催化剂。
• “Dibutylmagnesium”, a convenient reagent for the synthesis of useful organic magnesium reagents MgA2 including cyclopentadienyls, aryloxides, and amides. Preparation of Zr(C5H5)Cl3. X-ray structure of [{μ-N(SiMe)3C6H4N}(SiMe3)-o(OEt2)]2
  作者：Alan W. Duff、Peter B. Hitchcock、Michael F. Lappert、Richard G. Taylor、John A. Segal

  DOI：10.1016/0022-328x(85)80298-9

  日期：1985.9

  C5H4SiMe3), V [A = C5H3(SiMe3)2], VII (A = OC6H2Bu2t-2,6-Me-4), and X [A2 = N(SiMe3)C6H4N(SiMe3)-o(OEt2)]. The value of such compounds MgA2 as mild ligand transfer reagents is illustrated by the synthesis of Zr(C5H3X2)Cl3 (X = H or SiMe3). Compound X was isolated from OEt2 solution as the crystalline dimer with two o-(SiMe3)C6H4(SiMe3) ligands bridging two magnesium atoms and a terminal OEt2 ligand

  已发现可溶于正庚烷的“二丁基镁”（I）（可商购获得的材料，是通过将LiBu s添加到MgBu n Cl中并随后添加约5％MgOct 2 n来制备的）获得许多有机镁化合物的原料。这可以通过与许多质子化合物HA发生反应来说明，以提供高收率的Mg（C 5 H 5）2，Mg（C 5 H 4 Me）2或新化合物MgA 2：IV（A = C 5 H 4 SiMe 3），V [A = C 5 H 3（SiMe 3）2 ]，VII（A = OC 6 H 2 Bu 2 t -2,6-Me-4）和X [A 2 = N（SiMe 3）C 6 H 4 N（SiMe 3）-o（OEt 2）]。Zr（C 5 H 3 X 2）Cl 3（X = H或SiMe 3）的合成说明了这种化合物MgA 2作为温和的配体转移试剂的价值。从OEt 2溶液中分离出化合物X，为具有两个邻位- （SiMe3）C 6 H 4（SiMe 3）配体桥接两个镁原子和一个末端OEt
• Cyclopentadienylderivate von Aluminium(I)
  作者：Helmut Sitzmann、Michael F Lappert、Carsten Dohmeier、Christoph Üffing、Hansgeorg Schnöckel

  DOI：10.1016/s0022-328x(98)00555-5

  日期：1998.6

  spectroscopy to investigate and characterize new cyclopentadienylaluminum(I) derivatives formed in the reaction of AlX (X=Cl, Br, Cp* (=C5Me5)) with MRn (n=1: M=alkaline metal; n=2: M=Mg; R=cyclopentadienyl derivative (CpD), N(SiMe3)2): formation of new monomeric and tetrameric Al(I) species and X-ray structure analysis of a new aluminum(I) compound with an Al4-tetrahedron.

  27 Al-NMR光谱研究和表征在AlX（X = Cl，Br，Cp *（= C 5 Me 5））与MR n（n = 1：M =碱金属）反应中形成的新的环戊二烯基铝（I）衍生物；n = 2：M = Mg； R =环戊二烯基衍生物（Cp D），N（SiMe 3）2）：形成新的单体和四聚体Al（I）物种，并对新的Al（I）进行X射线结构分析与Al 4-四面体的化合物。
• Metallocene-catalyzed polyalpha-olefins
  申请人：ExxonMobil Chemical Patents Inc.

  公开号：US10968290B2

  公开（公告）日：2021-04-06

  Unsaturated and hydrogenated polyalpha-olefin products can be made with a high selectivity toward vinylidenes and tri-substituted vinylenes combined, a high selectivity toward vinylidenes, and a low selectivity toward 1,2-di-substituted vinylenes by using a catalyst system comprising a metallocene compound having the following structure in the polymerization reaction:

  可以使用具有以下结构的茂金属化合物的催化剂体系，在聚合反应中制备具有高选择性朝向乙烯基和三取代乙烯基的不饱和和氢化聚α-烯烃产品，朝向乙烯基的高选择性，以及朝向1,2-二取代乙烯基的低选择性。