Cp(*)W(NO)(η(2)-CPhCH2)(CH2Si(CH3)3) | 164400-22-0

• 英文名称: Cp(*)W(NO)(η(2)-CPhCH2)(CH2Si(CH3)3)
• 英文别名: [(η5-C5Me5)W(NO)(CH2SiMe3)(η2-CH2CPh)]；Cp(*)W(NO)(CH2SiMe3)(η2-CPhCH2)
• CAS: 164400-22-0
• 化学式: C₂₂H₃₃NOSiW
• 分子量: 539.446
• InChiKey: RKHBLVQTPNDUMC-UHFFFAOYSA-N

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：

  Cp(*)W(NO)(η(2)-CPhCH2)(CH2Si(CH3)3) 、 丙腈 以 neat (no solvent) 为溶剂， 以68%的产率得到((CH3)5C5)W(NO)(η(3)-HNC(C2H5)=NC(=CHCH3)CH=CPh)
  参考文献：
  名称：

  Cp * W（NO）模板介导的配体精加工：将小分子逐步掺入钨乙烯基片段中

  摘要：

  在不饱和，含杂原子的化合物（例如酯和腈）的存在下，烷基乙烯基络合物Cp * W（NO）（CH 2 SiMe 3）（CPh CH 2）（1）的热定量提供还原偶联的金属环产物。它们通过分子内重排或与添加的捕获剂的分子间反应被捕获为18e络合物。这些metallacycles的性质是与乙炔复杂Cp的中间性一致* W（NO）（η 2 -CPh⋮CH）（阿）原位衍生自森的还原消除4从1。用酯ROAC（R =甲基，乙基），还原偶联和C-O键断裂产生了含有烷氧化物的oxametallacyclopentadiene络合物的Cp * W（NO）（η 2 - Ö C（Me）的CH Ç PH）（OR）（2，R = Me；3，R = Et）。热分解1在RCN（R =甲基，乙基，我PR）含有少量过量的R'OH的产生各自的氢氧化物或醇盐化合物的Cp * W（NO）（η 2 - Ñ ħ C（R）CH Ç PH） （OR'）（4，R

  DOI：

  10.1021/om971080r
• 作为产物：
  描述：

  、 (η(5)-C5Me5)W(NO)(CH2SiMe3)Cl 以 四氢呋喃 为溶剂， 生成 Cp(*)W(NO)(η(2)-CPhCH2)(CH2Si(CH3)3)
  参考文献：
  名称：

  Facile Thermal Reactivity of Cp*W(NO)(CH2SiMe3)(CPh:CH2): Unique Alkane C-H Activation under Mild Conditions

  摘要：

  DOI：

  10.1021/ja00116a040

文献信息

• Hydrocarbon C−H Bond Activation by a Tungsten Acetylene Complex
  作者：Jeff D. Debad、Peter Legzdins、Sean A. Lumb、Steven J. Rettig、Raymond J. Batchelor、Frederick W. B. Einstein

  DOI：10.1021/om9904450

  日期：1999.8.1

  of 1 under thermolysis conditions regioselectively affords Cp*W(NO)(η3-endo-CH2C(Me)C(Me)CH2(η1-CPhMe)) (15). Attempts to trap acetylene complex A with PMe3 result in the formation of the metallacyclopropane complex Cp*W(NO)(CH2SiMe3)(η2-CH2CPh(PMe3)) (16). All new complexes have been characterized by conventional spectroscopic methods, and the solid-state molecular structures of compounds 11, 15, and

  CP的热激活* W（NO）（η 2 -CPhCH 2）（CH 2森达3）（1）在纯烃溶液中瞬时产生的CP * W（NO）（η 2 -PhC⋮CH）（阿），其随后激活溶剂CH键。例如，热解1中的苯溶液产生定量的CP * W（NO）（η 2 -CPhCH 2）（PH）（2）。的热解1中的甲基取代的芳烃，例如甲苯或解p， -米- ，或ö二甲苯提供通式CP的芳基和苄基乙烯基配合物的混合物* W（NO）（η 2 -CPhCH 2）（芳基）中，CP * W（NO）（η 2 -CPhCH 2）（η 1 -苄基）或CP * W（NO）（η 2 -苄基）（η 1 -CPh CH 2）。类似地，热解1中（ME 3 Si）的2 ö得到的CP * W（NO）（η 2 -CPhCH 2）（CH 2森达2 OSiMe 3）（10）。机理和动力学研究支持的建议，即形成一个从1通过消去硅烷的是在这些反应中的速率控制过程。
• Transformations of Cyclic Olefins Mediated by Tungsten Nitrosyl Complexes
  作者：Miriam S. A. Buschhaus、Craig B. Pamplin、Ian J. Blackmore、Peter Legzdins

  DOI：10.1021/om800384z

  日期：2008.9.22

  focus on Cp*W(NO)(CH2CMe3)2 (1) and Cp*W(NO)(CH2SiMe3)(η2-CPhCH2) (2). Upon thermolysis, these precatalysts oligomerize simple cyclic olefins, from cyclopentene to cyclooctene, into ring-retaining oligomers as high as dodecamers (depending on the substrate) with remaining sites of unsaturation. Precatalyst initiation involves the coupling of one equivalent of the substrate with the reactive 16e intermediate

  本报告介绍了一些研究，这些研究阐明了一系列钨预催化剂对环烯烃低聚的性质，程度和机理的影响，特别是对CP * W（NO）（CH 2 CMe 3）2（1）和CP的研究。 * W（NO）（CH 2森达3）（η 2 -CPhCH 2）（2）。在热解后，这些预催化剂将简单的环状烯烃（从环戊烯到环辛烯）低聚为高达十二聚体（取决于底物）的环保留低聚物，并保留不饱和位点。预催化剂引发涉及一个当量底物与反应16耦合È中间由前段催化剂热产生的（即，通过一个亚烷基1或η 2 -alkyne络合物2）中，随后在所述金属的配位层的连接配位体的重排要么烯烃或二烯（具有两个同时损失氢原子）。重排的配体从金属中心作为两个当量的底物配位体移位，以形成假定的双烯烃络合物CP * W（NO）（环烯烃）2，其表示预催化剂催化循环的收敛入口点。配位烯烃经历金属介导的偶联以形成金属环戊烷络合物。该金属环然后经历β氢活化和还原消除，以生成η
• 1-Metallacyclopropene Complexes and η¹-Vinyl Complexes Containing the Cp*W(NO) Fragment
  作者：Peter Legzdins、Sean A. Lumb、Steven J. Rettig

  DOI：10.1021/om990178y

  日期：1999.8.1

  The solid-state molecular structure of Cp*W(NO)(CH2SiMe3)(eta(2)-CPhCH2) reveals that the vinyl ligand in this complex exists in a distorted form in the solid state that cannot be readily described by either of the classic eta(1)-vinyl or 1-metallacyclopropene limiting structures, by comparison to other crystallographically characterized vinyl complexes reported in the literature. However, the NMR parameters for the CPhCH2 fragment in this complex are characteristic of those of a 1-metallacyclopropene unit. In addition to these studies, a series of vinyl-containing species of the general formulas Cp*W(NO)(eta(2)-CPhCH2)(X) and Cp*W(NO)(eta(1)-CPh=CH2)(LX) (X = Cl, OTf; LX = O2CPh, (NHBu)-Bu-t, (PPh3)(H)) has been prepared, and the solid-state metrical parameters and solution NMR spectroscopic properties of these complexes have been examined and compared to those of other vinyl-containing complexes reported in the literature. It has been found that the nature of the tungsten-vinyl interaction in these compounds is dependent upon the donor strength of the one-electron (1e) X or 3e LX donor ligands that are also present in the tungsten coordination sphere.
• Reactions of Two Cp*W(NO) Complexes with Heterocyclic Olefins
  作者：Miriam S. A. Buschhaus、Christopher J. Semiao、Peter Legzdins

  DOI：10.1021/om800724d

  日期：2009.2.23

  Cp*W(NO)(CH2CMe3)(2) (1) and Cp*W(NO)(CH2SiMe3)(eta(2)-CPhCH2) (2), two complexes which initiate the catalytic ring-retaining oligomerization of cyclic olefin substrates from cyclopentene to cyclooctene, have been reacted with analogous heteroatom-containing cyclic olefins under thermolytic conditions. These reactions with 2,5-dihydrofuran, 3,4-dihydro-2H-pyran, and 1,2,3,6-tetrahydropyridine do not result in the formation of oligomeric organic products but, rather, afford organometallic complexes resulting from alternate modes of substrate reactivity, such as ring-opening C-O bond cleavage and N-H activation.
• Generation and Reactivity of CpW(NO)(CH2SiMe3)H, a 16-Valence-Electron Alkyl Hydride Complex
  作者：Jeff D. Debad、Peter Legzdins、Sean A. Lumb、Raymond J. Batchelor、Frederick W. B. Einstein

  DOI：10.1021/om00005a061

  日期：1995.5

  Treatment of solutions of Cp*W(NO)(CH(2)SiMe(3))(2) with H-2 generates in situ the reactive 16-valence-electron alkyl hydride Cp*W(NO)(CH(2)SiMe(3))H, formed by hydrogenolysis of one of the W-C sigma-bonds of the dialkyl reactant. The Lewis-acidic hydride complex has not yet been isolated, but its existence has been inferred on the basis of the varied chemical reactions that it undergoes when generated in the presence of reactive substrates. PPh(3) affords the orthometalated complex Cp*W(NO)(H)(PPh(2)C(6)H(4)) as a yellow crystalline solid probably via the 18-electron adduct Cp*W(NO)(CH(2)SiMe(3))(PPh(3))H. Consistently, the same reaction effected with PPh(3)-d(15) results in complete deuteration of the hydride position in the product. Acyclic, conjugated dienes such as butadiene or 2,3-dimethyl-1,3-butadiene afford Cp*W(NO)(eta(4)-trans-diene) complexes. The characteristic chemistry of Cp*W(NO)(CH(2)SiMe(3))H is, however, dominated by the ability of its W-H link to insert unsaturated linkages, the regioselectivity of the insertions indicating that the hydride Ligand is hydridic in nature. For instance, insertion of acetonitrile affords the ethylideneamido complex Cp(*)W(NO)(CH(2)SiMe(3))(N=CHMe), which is isolable as a diastereomeric pair. Similarly, insertions of organic reagents containing carbonyl (O=C) or imine (HN=C) functional groups produce the corresponding alkyl alkoxide or alkyl amide products, respectively, in virtually quantitative yields. Phenylacetylene affords the novel alkyl alkenyl compound Cp*W(NO)(CH(2)SiMe(3))(CPh=CH2), which is thermally unstable and isolable in only low yields. Insertions into the W-H bond by other olefinic substrates are successful only if the unsaturated hydrocarbon also contains a Lewis-base functional group. Thus, propargylamine and allylamine produce the related metallacyclic complexes Cp*W(NO)(CH(2)SiMe(3))(NH2CH2CHCH) and Cp*W(NO)(CH(2)SiMe(3))(NH2CH2CH2CH2), respectively. Treatment of Cp*W(NO)(CH(2)SiMe(3))(2) with H-2 in the presence of allyl alcohol does not produce an oxometallacycle, but rather affords the allylalkoxo complex resulting from the alcohol simply functioning as a protonic acid toward the dialkyl reactant. The solid-state molecular structures of Cp*W(NO)(CH(2)SiMe(3))(N=CHMe) and Cp*W(NO)(CH(2)SiMe(3))(NH2CH2CH2CH2) have been established by single-crystal X-ray crystallographic analyses. Crystals of Cp*W(NO)(CH(2)SiMe(3))(N=CHMe) are monoclinic of space group P2(1)/n: a = 9.515(2) Angstrom; b = 21.946(3) Angstrom; c = 9.552(2) Angstrom; Z = 4; V = 1946.8 Angstrom(3); T = 200 K; R(f) = 0.029 for 2035 data (I-0 greater than or equal to 2.5 sigma(I-0)) and 106 variables. Crystals of Cp*W(NO)(CH(2)SiMe(3))(NH2CH2CH2CH2) are orthorhombic of sp ace group P2(1)2(1)2(1): a 11.417(4) Angstrom; b = 13.178(2) Angstrom; c 13.804(4) Angstrom; Z = 4; V = 2076.9 Angstrom(3); T = 200 K; R(f) = 0.020 for 2420 data (I-0 greater than or equal to 2.5 sigma(I-0)) and 208 variables.