[(pentamethylcyclopentadienyl)₂yttrium(III)(μ-Ph)₂BPh₂] | 306776-06-7

• 英文名称: [(pentamethylcyclopentadienyl)₂yttrium(III)(μ-Ph)₂BPh₂]
• 英文别名: [(C₅Me₅)₂Y][(μ-Ph)₂BPh₂]；(C₅Me₅)₂Y(μ-Ph)₂BPh₂；Cp*₂Y(BPh₄)；[(pentamethylcyclopentadienyl)2Y][(μ-Ph)2BPh2]；[(C5Me5)2Y][(μ-Ph)2BPh2]
• CAS: 306776-06-7
• 化学式: C₄₄H₅₀BY
• 分子量: 678.598
• InChiKey: FAMRPAUXJIQHBL-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：

  [(pentamethylcyclopentadienyl)₂yttrium(III)(μ-Ph)₂BPh₂] 、 丙酮 以 苯 为溶剂， 以91%的产率得到[(C5Me5)2Y(acetone)2][BPh4]
  参考文献：
  名称：

  三价稀土金属茂阳离子[（C 5 Me 5）2 Ln] [（μ-Ph）2 BPh 2 ]的四苯基硼酸酯配合物的配位和还原化学

  摘要：

  稀土金属茂阳离子[[C 5 Me 5）2 Ln] [（μ-Ph）2 BPh 2 ]（Ln = Y，1 ; Sm，2）的四苯基硼酸盐的反应活性已通过用f元素络合物进行还原反应，以在还原之前探测金属与底物的相互作用。结果与NaN的3，1-金刚烷基叠氮化物，丙酮，二苯甲酮，菲咯啉，吡啶，偶氮苯，和吩嗪中描述。不仅分离了配位化合物，而且还观察到底物减少了（BPh 4）-。配合物1与NaN 3反应以形成叠氮化物[（C 5我5）2 YN 3 ] X，3，其结晶为[（C 5我5）2 Y（μ-N 3）] 3，4从获得时，1和1-金刚烷基叠氮化物。2类似物[（C 5 Me 5）2 SmN 3 ] x，5可以类似地由2和NaN 3制备，并由MeCN结晶为[（C 5 Me 5）2 SM（NCMe）（μ-N 3）] 3，6，和{[（C 5我5）2的Sm（μ-N 3）] [（C 5我5）2 SM（NCMe）（μ-N

  DOI：

  10.1021/ic2000409
• 作为产物：
  描述：

  triethylammonium tetraphenylborate 、 (C₅Me₅)₂Y(μ-H)(μ-η¹:η⁵-CH₂C₅Me₄)Y(C₅Me₅) 以 苯 为溶剂， 反应 0.17h， 以87%的产率得到[(pentamethylcyclopentadienyl)₂yttrium(III)(μ-Ph)₂BPh₂]
  参考文献：
  名称：

  Reactivity of the Y³⁺ Tuck-Over Hydride Complex, (C₅Me₅)₂Y(μ-H)(μ-CH₂C₅Me₄)Y(C₅Me₅)

  摘要：

  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]Y{mu-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.

  DOI：

  10.1021/om300546t

文献信息

• Synthesis, Structure, and Reactivity of the Ethyl Yttrium Metallocene, (C₅Me₅)₂Y(CH₂CH₃), Including Activation of Methane
  作者：Matthew R. MacDonald、Ryan R. Langeslay、Joseph W. Ziller、William J. Evans

  DOI：10.1021/jacs.5b08597

  日期：2015.11.25

  (C5Me5)(2)Y(mu-Ph)(2)BPh2, 1, reacted with ethyllithium at -15 degrees C to make (C5Me5)(2)Y(CH2CH3), 2, which is thermally unstable at room temperature and formed the C-H bond activation product, (C5Me5)(2)Y(mu-H)(mu-eta(1):eta(5)-CH2C5Me4)Y(C5Me5), 3, containing a metalated (C5Me5)(1-) ligand. Spectroscopic evidence for 2 was obtained at low temperature, and trapping experiments with (PrNC)-Pr-i-(NPr)-Pr-i and CO2 gave the Y-CH2CH3 insertion products, (C5Me5)(2)Y-[(PrNC)-Pr-i(Et)(NPr)-Pr-i-kappa N-2,N'], 4, and [(C5Me5)(2)Y(mu-O2CEt)](2), 5. Although 2 is highly reactive, low temperature isolation methods allowed the isolation of single crystals which revealed an 82.6(2)degrees Y-CH2-CH3 bond angle consistent with an agostic structure in the solid state. Complex 2 reacted with benzene and toluene to make (C5Me5)(2)YPh, 7, and (C5Me5)(2)YCH2Ph, 8, respectively. The reaction of 2 with [(C5Me5)(2)YCl](2) formed (C5Me5)(2)Y(mu-Cl)(mu-eta(1):eta(5)-CH2C5Me4)Y(C5Me5) in which a (C5Me5)(1-) ligand was metalated. C-H bond activation also occurred with methane which reacted with 2 to make [(C5Me5)(2)YMe](2), 9.

  (C5Me5)(2)Y(mu-Ph)(2)BPh2, 1，与乙基锂在-15°C下反应生成(C5Me5)(2)Y( ), 2。该化合物在室温下热力学不稳定，并形成了C-H键活化产物(C5Me5)(2)Y(mu-H)(mu-eta(1):eta(5)- C5Me4)Y(C5Me5), 3，其中含有一个金属化的(C5Me5)(1-)配体。通过低温下的光谱分析获得了2的证据，并与(PrNC)-Pr-i-(NPr)-Pr-i和CO2进行捕捉实验，得到了Y- 插入产物：(C5Me5)(2)Y-[(PrNC)-Pr-i(Et)(NPr)-Pr-i-kappa N-2,N'], 4，和[(C5Me5)(2)Y(mu-O2CEt)](2), 5。尽管2具有高度反应性，但低温分离方法允许分离出单晶，揭示了一个82.6(2)度的Y-CH2-CH3键角，这与固体状态下的agostic结构一致。2与苯和甲苯反应分别生成(C5Me5)(2)YPh, 7，和(C5Me5)(2)Y Ph, 8。2与[(C5Me5)(2)YCl](2)反应生成(C5Me5)(2)Y(mu-Cl)(mu-eta(1):eta(5)- C5Me4)Y(C5Me5)，其中(C5Me5)(1-)配体被金属化。甲烷的C-H键活化也与2反应，生成[(C5Me5)(2)YMe](2), 9。
• Planar Trimethylenemethane Dianion Chemistry of Lanthanide Metallocenes:  Synthesis, Structure, Density Functional Theory Analysis, and Reactivity of [(C₅Me₅)₂Ln]₂[μ-η³:η³-C(CH₂)₃] Complexes
  作者：William J. Evans、Timothy M. Champagne、Joseph W. Ziller、Nikolas Kaltsoyannis

  DOI：10.1021/ja0645988

  日期：2006.12.1

  metals from La to Y to examine the effects of radial size on structure and to provide closed shell examples for direct comparison with density functional theory (DFT) calculations. Synthetic routes to 1-4 have been expanded from the [(C5Me5)2Ln][(mu-Ph)2BPh2]/neopentyl lithium reaction involving beta-methyl elimination to a [(C5Me5)2Ln][(mu-Ph)2BPh2]/isobutyl lithium route. The synthetic pathways are sensitive

  镧系金属茂 [(C5Me5)2Ln]2[mu-eta3:eta3-C(CH2)3] (Ln = Sm, 1; La, 2; Pr, 3; Nd, 4; Y, 5) 已经通过合成从 La 到 Y 的金属的例子来检查径向尺寸对结构的影响，并提供闭壳例子以直接与密度泛函理论 (DFT) 计算进行比较。合成路线 1-4 已从 [(C5Me5)2Ln][(mu-Ph)2BPh2]/新戊基锂反应扩展到 [(C5Me5)2Ln][(mu-Ph)2BPh2] /异丁基锂路线。合成途径对金属半径敏感。为了获得 5，合成了甲基烯丙基复合物 (C5Me5)2Y[ C(Me) ],6，并用 [(C5Me5)2YH]x 处理。在 Lu 的情况下，新戊基复合物 [(C5Me5)2Lu C(CH3)3]x, 7, 被隔离而不是 TMM 产品。X 射线晶体学表明，每个复合物中平面 TMM 二价阴离子的度量参数是相似的。结构数据与闭壳镧和镥配合物的
• Scandium and yttrium metallocene borohydride complexes: comparisons of (BH4)1−vs. (BPh4)1− coordination and reactivity
  作者：Selvan Demir、Nathan A. Siladke、Joseph W. Ziller、William J. Evans

  DOI：10.1039/c2dt30861d

  日期：——

  3], 8. Structural information was also obtained on the borohydride derivatives, (C5Me4H)2Sc(μ-H)2BC8H14, 9, and (C5Me5)2Sc(μ-H)2BC8H14, 10, obtained from 9-borabicyclo(3.3.1)nonane (9-BBN) and (C5Me4R)2Sc(η3-C3H5), where R = H, 11; Me, 12. The preference of the metals for borohydride over tetraphenylborate binding was shown by the facile displacement of (BPh4)1− in 3, 4, 7, and 8 by (BH4)1− to make

  研究了可合成获得的硼氢化物配合物（C 5 Me 4 H）2 Ln（THF）（BH 4）和（C 5 Me 5）2 Ln（THF）（BH 4）（Ln = Sc，Y）作为前体的替代物在LnA 2 A'/ M还原反应中使用的大量使用的四苯基硼酸酯类似物[（C 5 Me 4 H）2 Ln] [BPh 4 ]和[（C 5 Me 5）2 Ln] [BPh 4 ] =阴离子； M =碱金属），生成“ LnA 2”反应性和降低的形式配合物二氮[（C 5 - [R 5）2（THF）X LN] 2（μ-η 2：η 2 -N 2）（X = 0，1）。硼氢化钇（C 5 Me 4 H）2 Y（THF）（μ-H）3 BH，1和（C 5 Me 5）2 Y（THF）（μ-H）2 BH 2的晶体结构，2，确定为与那些钇四苯基硼酸盐的，[（C比较5我4 H） 2 Y] [（（μ-Ph） 2 BPh 2 ]， 3和[（C 5 Me
• Synthesis and structure of nitrile-solvated rare earth metallocene cations [Cp2Ln(NCR)3][BPh4] (Cp = C5Me5, C5H4SiMe3; R = Me, Bu, Ph)
  作者：Jordan F. Corbey、David H. Woen、Joseph W. Ziller、William J. Evans

  DOI：10.1016/j.poly.2015.09.002

  日期：2016.1

  4-Gd). In each case, only three nitriles are found to coordinate and the metallocenes are bent with (C5Me5 ring centroid)–metal–(C5Me5 ring centroid) angles of 137–140°. The THF adduct, [(C5Me5)2La(NCMe)2(THF)][BPh4], 5-La, was also crystallographically characterized. A similar result was observed with the yttrium metallocene of the trimethylsilyl-containing ligand (C5H4SiMe3)1−: coordination of only three

  摘要研究了MeCN，tBuCN和PhCN与阳离子稀土金属茂配合物[（C5Me5）2Ln] [（μ-Ph）2BPh2]，1-Ln（Ln = Y，La，Gd）的配位化学确定腈配位将如何影响茂金属的几何形状。[[C5Me5）2Ln（NCMe）3] [BPh4]（2-Y，2-Gd），[（C5Me5）2Y（NCtBu）3] [BPh4]（3-Y）的晶体学几何确定是可能的[（C5Me5）2Ln（NCPh）3] [BPh4]（4-La，4-Gd）。在每种情况下，仅发现三个腈进行配位，并且茂金属以（C5Me5环质心）-金属-（C5Me5环质心）角度为137-140°弯曲。还结晶表征了THF加合物[（C5Me5）2La（NCMe）2（THF）] [BPh4]，5-La。使用含三甲基甲硅烷基的配体（C5H4SiMe3）1-的钇金属茂观察到了类似的结果：
• Coupling of Nitric Oxide and Release of Nitrous Oxide from Rare-Earth-Dinitrosyliron Complexes
  作者：Arun Kumar Bar、María José Heras Ojea、Jinkui Tang、Richard A. Layfield

  DOI：10.1021/jacs.9b13571

  日期：2020.3.4

  [(NacNacAr)Fe(NO)2]- (Ar = mesityl, 2,6-diisopropylphenyl) results in formation of the isonitrosyl-bridged DNICs [(Cp*)2M(μ-ON)2Fe(NacNacAr)]. When Ar = 2,6-diisopropylphenyl, coupling of the NO ligands and release of N2O occurs. Two factors contribute to this pre-viously unobserved DNIC reactivity mode. Firstly, the oxophilic rare-earth elements drive the formation of isonitrosyl bonds, forcing the DNIC nitrogen

  将路易斯酸性 [Cp*2M]+ (M = Y, Gd) 添加到二亚硝基硅烷配合物 (DNICs) [(NacNacAr)Fe(NO)2]-（Ar = 甲基，2,6-二异丙基苯基）导致形成异亚硝基桥接的 DNIC [(Cp*)2M(μ-ON)2Fe(NacNacAr)]。当 Ar = 2,6-二异丙基苯基时，会发生 NO 配体的偶联和 N2O 的释放。有两个因素促成了这种以前未观察到的 DNIC 反应模式。首先，亲氧稀土元素驱动异亚硝基键的形成，迫使 DNIC 氮原子靠近。其次，庞大的取代基进一步挤压了 DNIC，最终克服了 NO 耦合的障碍，并证明了 消除可以从单个铁中心发生。