(C₅Me₅)₂Y(C≡CPh)(tetrahydrofuran) | 1333210-70-0

• 英文名称: (C₅Me₅)₂Y(C≡CPh)(tetrahydrofuran)
• 英文别名: (C₅Me₅)₂Y(C≡CPh)(THF)；(C5Me5)2Y(C.ident.CPh)(THF)
• CAS: 1333210-70-0
• 化学式: C₃₂H₄₃OY
• 分子量: 532.599
• InChiKey: TUVBXBWQELODNU-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：

  N,N′-二叔丁基碳二亚胺 、 (C₅Me₅)₂Y(C≡CPh)(tetrahydrofuran) 以 甲苯 为溶剂， 以68%的产率得到(C5Me5)2Y[(t)BuNC(C.ident.CPh)N(t)Bu-κ2N,N']
  参考文献：
  名称：

  C–H Activation via Carbodiimide Insertion into Yttrium–Carbon Alkynide Bonds: An Organometallic Alder-ene Reaction

  摘要：

  The yttrium alkynide (C5Me5)(2)Y(C CPh)(THF), 1, and the related trienediyl [(C5Me5)(2)Y](2)(mu-eta(2):eta(2)-PhC=C=C=CPh), 2, can be isolated from the reaction of (C5Me5)(2)Y(eta(3)-CH2CHCH2)(THF) with phenylacetylene in THF and hexane, respectively. Complex 1 reacts with (BuN)-Bu-t=C=(NBu)-Bu-t to afford the conventional amidinate insertion product (C5Me5)(2)Y[(BuNC)-Bu-t(C CPh)(NBu)-Bu-t-kappa N-2,N'], 3. However, the analogous reaction with iso-propyl and cyclohexyl carbodiimides involves C-H activation and forms the iminovinyl complexes (C5Me5)(2)Y[C(=CHPh)C(N=CMe2)=(NPr)-Pr-t-kappa C-2,N], 4, and (C5Me5)(2)Y{C(=CHPh)C[N=C(CH2)(5)]=NCH(CH2)(5)-kappa C-2,N}, 5, respectively. The reaction is formally a variation of the Alder-ene reaction in which a C-H bond of the carbodiimide (ene) is activated and transferred to the alkynide ligand (enophile) bound to yttrium. The trienediyl 2 reacts with iso-propyl carbodiimide via conventional insertion to form a bis(amidinate) product with a trienediyl linker, namely, (C5Me5)(2)Y-[mu-kappa(2)-((PrN)-Pr-i)(2)C-C(Ph)=C=C=C(Ph)-C((NPr)-Pr-i)(2)]Y(C5Me5)(2), 6. The alkynide ligand in 1 is also modified in the reaction with benzylcyanide that forms an unusual insertion product, the amidonitrile complex [(C5Me5)(2)Y{mu-N(H)C(CH2Ph)=C[C(Ph)=CHPh]C N}](2), 7.

  DOI：

  10.1021/om200419k
• 作为产物：
  描述：

  (C5Me5)2Y(η3-CH2CHCH2)(THF) 、 苯乙炔 以 四氢呋喃 为溶剂， 以30%的产率得到(C₅Me₅)₂Y(C≡CPh)(tetrahydrofuran)
  参考文献：
  名称：

  C–H Activation via Carbodiimide Insertion into Yttrium–Carbon Alkynide Bonds: An Organometallic Alder-ene Reaction

  摘要：

  The yttrium alkynide (C5Me5)(2)Y(C CPh)(THF), 1, and the related trienediyl [(C5Me5)(2)Y](2)(mu-eta(2):eta(2)-PhC=C=C=CPh), 2, can be isolated from the reaction of (C5Me5)(2)Y(eta(3)-CH2CHCH2)(THF) with phenylacetylene in THF and hexane, respectively. Complex 1 reacts with (BuN)-Bu-t=C=(NBu)-Bu-t to afford the conventional amidinate insertion product (C5Me5)(2)Y[(BuNC)-Bu-t(C CPh)(NBu)-Bu-t-kappa N-2,N'], 3. However, the analogous reaction with iso-propyl and cyclohexyl carbodiimides involves C-H activation and forms the iminovinyl complexes (C5Me5)(2)Y[C(=CHPh)C(N=CMe2)=(NPr)-Pr-t-kappa C-2,N], 4, and (C5Me5)(2)Y{C(=CHPh)C[N=C(CH2)(5)]=NCH(CH2)(5)-kappa C-2,N}, 5, respectively. The reaction is formally a variation of the Alder-ene reaction in which a C-H bond of the carbodiimide (ene) is activated and transferred to the alkynide ligand (enophile) bound to yttrium. The trienediyl 2 reacts with iso-propyl carbodiimide via conventional insertion to form a bis(amidinate) product with a trienediyl linker, namely, (C5Me5)(2)Y-[mu-kappa(2)-((PrN)-Pr-i)(2)C-C(Ph)=C=C=C(Ph)-C((NPr)-Pr-i)(2)]Y(C5Me5)(2), 6. The alkynide ligand in 1 is also modified in the reaction with benzylcyanide that forms an unusual insertion product, the amidonitrile complex [(C5Me5)(2)Y{mu-N(H)C(CH2Ph)=C[C(Ph)=CHPh]C N}](2), 7.

  DOI：

  10.1021/om200419k

文献信息

• Reactivity of the Y³⁺ Tuck-Over Hydride Complex, (C₅Me₅)₂Y(μ-H)(μ-CH₂C₅Me₄)Y(C₅Me₅)
  作者：Benjamin M. Schmiege、Megan E. Fieser、Joseph W. Ziller、William J. Evans

  DOI：10.1021/om300546t

  日期：2012.8.13

  The trivalent yttrium tuck-over hydride complex, (C5Me5)(2)Y(mu-H)(mu-eta(1):eta(5)-CH2C5Me4)Y(C5Me5), 1, acts as a reductant in reactions in which the (mu-H)(-) hydride ligand and the bridging Y-C alkyl anion linkage in the mu-eta(1):eta(5)-CH2C5Me4)(2-) ligand combine to form a C-H bond in (C5Me5)(-) and deliver two electrons to a substrate. Complex 1 reacts with PhSSPh, AgOTf (OTf = OSO2CF3), and Et3NHBPh4 to form [(C5Me5)(2)Y(mu-SPh)](2), [(C5Me5)(2)Y(mu-OTf)](2), and (C5Me5)(2)Y(mu-Ph)(2)BPh2, respectively. The reactivity of the Y-H and Y-CH2C5Me4 linkages in 1 was probed via carbodiimide insertion reactions. (PrN)-Pr-i=C=(NPr)-Pr-i inserts into both Y-H and Y-C bonds to yield (C5Me5)[(PrNC)-Pr-i(H)(NPr)-Pr-i]Ymu-eta(5)-C5Me4CH2[(PrNCNPr)-Pr-i-Pr-i]}Y(C5Me5)(2). Carbodiimide insertion with [(C5Me5)(2)YH](2), 2, was also examined for comparison, and (C5Me5)(2)Y[(PrNC)-Pr-i(H)(NPr)-Pr-i-kappa N-2,N'] was isolated and structurally characterized. To examine the possibility of selective reactivity of the bridging ligands, mu-H versus mu-CH2C5Me4, trimethylsilylchloride was reacted with 1, and the tuck-over chloride complex, (C5Me5)(2)Y(mu-Cl)(mu-eta(1):eta(5)-CH2C5Me4)Y(C5Me5), was isolated.