Cp*₂Y(Me)(thf) | 109364-77-4

• 英文名称: Cp*₂Y(Me)(thf)
• CAS: 109364-77-4
• 化学式: C₂₅H₄₁OY
• 分子量: 446.506
• InChiKey: SQGDKSIZIBMCTF-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*₂Y(Me)(thf) 在 吡啶 作用下， 以 氘代苯 为溶剂， 生成 (η5-C5Me5)2Y(η2-NC5H4)*THF
  参考文献：
  名称：

  钇碳键与活性氢分子的反应。一种有用的全甲基二茂铁衍生物的合成方法

  摘要：

  DOI：

  10.1021/om00153a004
• 作为产物：
  描述：

  四氢呋喃 、 以 四氢呋喃 、 正己烷 为溶剂， 以99%的产率得到Cp*₂Y(Me)(thf)
  参考文献：
  名称：

  Tetramethylaluminate and Tetramethylgallate Coordination in Rare-Earth Metal Half-Sandwich and Metallocene Complexes

  摘要：

  The synthesis of half-sandwich tetramethylaluminate complexes Cp*Y(AlMe4)(2) (Cp* = C5Me5) was achieved by applying two synthesis protocols: (a) protonolysis of Y(AlMe4)(3) with excess HCp* at ambient temperature; (b) alkylamide elimination using Cp*Y(NiPr2)(2)(THF) and trimethylaluminum at ambient temperature. The tetramethylgallate derivative Cp*Y(GaMe4)(2) was obtained from the equimolar reaction of Y(GaMe4)(3) with HCp* or by addition of 2 equiv of trimethylgallium to [Cp*YMe2](3). The half-sandwich complexes Cp*Y(MMe4)(2) (M = Al, Ga) display similar structural chemistry featuring highly fluxional methyl groups in solution and one planar and one atypically bent Y(mu-Me)(2)M moiety in the solid state. Complexes [CP*(2)Ln(MMe4)] (Ln = Y, La; M = Al, Ga) were synthesized from Ln(MMe4)(3) with excess HCp* at elevated temperature. Such metallocene complexes show the known monomer-dimer equilibria in solution, with the entropically disfavored dimer prevailing at low temperature. Dimeric [Cp*La-2(AlMe4)](2) and [Cp*Y-2(GaMe4)](2) as well as monomeric CP*La-2(GaMe4) were analyzed by X-ray diffraction.

  DOI：

  10.1021/om9007168
• 作为试剂：
  描述：

  甲基苯基硅烷 、 ((1S,2R)-1-Allyl-2-vinyl-cyclopentyloxy)-trimethyl-silane 在 Cp*₂Y(Me)(thf) 作用下， 以 环己烷 为溶剂， 反应 0.75h， 以88%的产率得到(3aS,7aR)-7-[(Methyl-phenyl-silanyl)-methyl]-3a-trimethylsilanyloxy-octahydro-indene
  参考文献：
  名称：

  Stereoselective Synthesis of Carbobicyclics via Organoyttrium-Catalyzed Sequential Cyclization/Silylation Reactions

  摘要：

  The sequential cyclization/silylation of 1,5-dienes and 1,6-dienes was effected under mild reaction conditions using catalytic quantities of Cp-2*YMe . THF. The process provides carbobicyclics in high yields and with excellent selectivities. The active catalyst is postulated to be Cp-2*YH . THF, which is generated in situ. A variety of alkenyl-substituted cyclopentane and cyclohexane substrates were examined. The high diastereoselectivities apparently originate fi om a preference for a chairlike transition structure that minimizes unfavorable steric interactions between the bulky Cp* ligands of the catalyst and the preexisting ring of the substrate. Acyclic triene precursors, 4-ethenyl-substituted 1,5-heptadienes and 5-ethenyl-substituted 1,8-nonadienes were also examined. These triene substrates, when exposed to the cyclization/silylation protocol, provide the strained trans-bicyclo[3.3.0]octanes and trans-decalin systems in high yield with excellent diastereoselectivity. The high selectivity is again attributed to the preference for a chairlike transition structure. The cyclized organosilane products isolated from these reactions were easily converted to the more versatile alcohols utilizing known oxidation methods.

  DOI：

  10.1021/jo9721352

文献信息

• The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*₂Y(MMe₃R)] (M = Al, Ga)
  作者：Martin Bonath、Dorothea Schädle、Cäcilia Maichle-Mössmer、Reiner Anwander

  DOI：10.1021/acs.inorgchem.1c02349

  日期：2021.10.4

  derivatives [Cp*2Y(MMe4)] (Cp* = C5Me5; M = Al, Ga) and Cp*2Y[Me3AlB(NDippCH)2}] (Dipp = C6H3iPr2-2,6) deprotonate benzene at elevated temperatures via the release of methane. The formation of [Cp*2Y(Me2MPh2)] (M = Al, Ga), Cp*2Y(MPh4) (M = Al, Ga), Cp*2Y[Me2AlPhB(NDippCH)2}], and Cp*2Y[AlPh3B(NDippCH)2}] can be controlled via the temperature applied. The activation temperature and formation of the coordinatively

  钇衍生物 [Cp* 2 Y(MMe 4 )] (Cp* = C 5 Me 5 ; M = Al, Ga) 和 Cp* 2 Y[Me 3 AlB(NDippCH) 2 }] (Dipp = C 6 H 3 i Pr 2 -2,6) 在升高的温度下通过释放甲烷使苯去质子化。[Cp* 2 Y(Me 2 MPh 2 )] (M = Al, Ga), Cp* 2 Y(MPh 4 ) (M = Al, Ga), Cp* 2 Y[Me 2 AlPhB( NDippCH) 2 }] 和 Cp* 2 Y[AlPh 3B(NDippCH) 2 }] 可以通过施加的温度进行控制。活化温度和配位不饱和“反应性”[Cp* 2 YMe] 的形成在很大程度上取决于可置换路易斯酸 [AlMe 3 ] 2、GaMe 3和 [Me 2 AlB(NDippCH) 2 }的配位强度] 2。因此，[Cp* 2 Y(AlMe
• Rare-earth-metallocene alkylaluminates trigger distinct tetrahydrofuran activation
  作者：Martin Bonath、Verena M. Birkelbach、Christoph Stuhl、Cäcilia Maichle-Mössmer、Reiner Anwander

  DOI：10.1039/d1cc03024h

  日期：——

  Lanthanocene Cp*₂La(AlMe₄) affords selective metalation of tetrahydrofuran to the 2-tetrahydrofuranyl derivative Cp*₂La(2-AlMe₃-OC₄H₇), while the yttrium reaction leads to THF degradation.

  Lanthanocene Cp*2La(AlMe4)可以选择性地使四氢呋喃金属化为2-四氢呋喃基衍生物Cp*2La(2-AlMe3-OC4H7)，而钇反应会导致THF降解。
• Rare‐Earth‐Metal‐Promoted Hydroalumination
  作者：Christoph Schädle、Reiner Anwander

  DOI：10.1002/ejic.201300504

  日期：2013.7

  oalane to act as a hydride transfer reagent in organolanthanide chemistry was investigated by probing its reactivity toward alkylyttrium complexes. Reaction with Cp*2YMe(thf) led to the isolation of the bimetallic complex Cp*2Y(μ-H)2Al(Me)[N(SiMe3)2] (Cp* = 1,2,3,4,5-pentamethylcyclopentadiene), whereas reaction with [Cp*YMe2]3 gave MeAl[N(SiMe3)2]2 as the only isolable hydride transfer product. The

  通过探测其对烷基钇配合物的反应性，研究了双（三甲基甲硅烷基）酰胺基丙烷在有机镧系元素化学中作为氢化物转移试剂的能力。与 Cp*2YMe(thf) 反应分离出双金属配合物 Cp*2Y(μ-H)2Al(Me)[N(SiMe3)2] (Cp* = 1,2,3,4,5-五甲基环戊二烯)，而与 [Cp*YMe2]3 反应得到 MeAl[N(SiMe3)2]2 作为唯一可分离的氢化物转移产物。二聚复合物 [Cp*YN(SiMe3)2}(μ-H)]2 代表上述反应的一种可能产物，其可以在结构上进行表征。使用 [YMe3]n 作为烷基钇源导致 Y[N(SiMe3)2]3 的分离，这显示了酰胺和氢化物转移之间的竞争。最后，测试了Cp*2Y(μ-H)2Al(Me)[N(SiMe3)2]和[YMe3]n在1-辛烯加氢铝化反应中的性能，
• Synthesis of permethylyttrocene alkyl complexes
  作者：Klaas H. Den Haan、Ytsen Wielstra、Johan J.W. Eshuis、Jan H. Teuben

  DOI：10.1016/0022-328x(87)80367-4

  日期：1987.4
• Metallorganische Verbindungen der Lanthanoide. 111. Synthese und Charakterisierung kationischer Metallocen-Komplexe der Lanthanoide. R�ntgenstrukturanalyse von [Cp2*Yb(THF)2][BPh4]
  作者：Herbert Schumann、J�rn Winterfeld、Markus R. Keitsch、Katja Herrmann、J�rg Demtschuk

  DOI：10.1002/zaac.19966220905

  日期：1996.9

  AbstractKationische Organolanthanoide des Typs [(C5H4R)2Sm(THF)2][BPh4] (R = tBu (1), SiMe3 (2)), [PyrSm(THF)][BPh4] (3) (Pyr* = NC4H2tBu2‐2,5), [CpLn‐(THF)2[BPh4] (Cp* = C5Me5; Ln = Y (4), Yb (5)) und [(C5Me4Et)2Ln(THF)2][BPh4] (Ln = Y (6), Sm (7)) wurden durch Oxidation der zweiwertigen Metallocene [(C5H4R)2Sm(THF)2] (R = tBu, SiMe3), [PyrSm(THF)], [CpYb(THF)] und [(C5Me4Et)2Sm(THF)] mit Ag[BPh4] und durch Protolyse der Lanthanoidalkomplexe [CpYMe(THF)], [CpYbCH(SiMe3)2] und [(C5Me4Et)2LnCH‐(SiMe3)2] (Ln = Y, Sm) mit [NEt3H][BPh4] hergestellt. Die 1H‐und 13C‐NMR‐Spektren der neuen Verbindungen werden diskutiert. 5 kristallisiert in der Raumgruppe P21/c mit a = 10.604(7), b = 21.749(3), c = 19.124(4), Å, β = 96.47(4)°, Z = 4 und V = 4383(3) Å3 (R = 0.0291 für 8517 beobachtete Reflexe mit Fo ≥ 4σ (Fo).