(Cy₃P)₂Ni(CO) | 1421355-65-8

• 英文名称: (Cy₃P)₂Ni(CO)
• 英文别名: (PCy3)2Ni(CO)
• CAS: 1421355-65-8
• 化学式: C₃₇H₆₆NiOP₂
• 分子量: 647.568
• InChiKey: JHQSNMYLRIRLGO-UHFFFAOYSA-N

计算性质

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

• 作为产物：
  描述：

  (2-naphtyl)bis(triphenylphosphine)nickel(II) chloride 以 四氢呋喃 、 丙酮 为溶剂， 反应 5.5h， 生成 (Cy₃P)₂Ni(CO)
  参考文献：
  名称：

  Combined Experimental and Theoretical Study on the Reductive Cleavage of Inert C–O Bonds with Silanes: Ruling out a Classical Ni(0)/Ni(II) Catalytic Couple and Evidence for Ni(I) Intermediates

  摘要：

  A mechanistic and computational study on the reductive cleavage of C-OMe bonds catalyzed by Ni(COD)(2)/PCy3 with silanes as reducing agents is reported herein. Specifically, we demonstrate that the mechanism for this transformation does not proceed via oxidative addition of the Ni(0) precatalyst into the C-OMe bond. In the absence of an external reducing agent, the in-situ-generated oxidative addition complexes rapidly undergo beta-hydride elimination at room temperature, ultimately leading to either Ni(0)-carbonyl- or Ni(0)-aldehyde-bound complexes. Characterization of these complexes by X-ray crystallography unambiguously suggested a different mechanistic scenario when silanes are present in the reaction media. Isotopic-labeling experiments, kinetic isotope effects, and computational studies clearly reinforced this perception. Additionally, we also found that water has a deleterious effect by deactivating the Ni catalyst via formation of a new Ni-bridged hydroxo species that was characterized by X-ray crystallography. The order in each component was determined by plotting the initial rates of the C-OMe bond cleavage at varying concentrations. These data together with the in-situ-monitoring experiments by H-1 NMR, EPR, IR spectroscopy, and theoretical calculations provided a mechanistic picture that involves Ni(I) as the key reaction intermediates, which are generated via comproportionation of initially formed Ni(II) species. This study strongly supports that a classical Ni(0)/Ni(II) for C-OMe bond cleavage is not operating, thus opening up new perspectives to be implemented in other related C-O bond-cleavage reactions.

  DOI：

  10.1021/ja311940s

文献信息

• Selective Reduction of CO₂ to a Formate Equivalent with Heterobimetallic Gold- - -Copper Hydride Complexes
  作者：Alexandra Hicken、Andrew J. P. White、Mark R. Crimmin

  DOI：10.1002/anie.201709072

  日期：2017.11.20

  A series of heterobimetallic complexes containing three‐center, two‐electron Au−H−Cu bonds have been prepared from addition of a parent gold hydride to a bent d10 copper(I) fragment. These highly unusual heterobimetallic complexes represent a missing link in the widely investigated series of neutral and cationic coinage metal hydride complexes containing Cu−H−Cu and M−H−M+ moieties (M=Cu, Ag). The

  通过将母体氢化物加到弯曲的d 10铜（I）片段上，可以制备出一系列包含三中心，两电子Au-H-Cu键的杂双金属配合物。这些高度不寻常的异双金属配合物代表了广泛研究的一系列含有Cu-H-Cu和M-H-M +部分（M = Cu，Ag）的中性和阳离子造币金属氢化物配合物中的缺失环节。定义明确的杂双金属氢化物配合物可将HBpin作为还原剂将CO 2转化为HCO 2 Bpin的预催化剂。杂双金属配合物对甲酸酯当量催化生产的选择性超过了母体单体第11组配合物的选择性。
• Controlled Photoredox Ring-Opening Polymerization of <i>O</i>-Carboxyanhydrides
  作者：Quanyou Feng、Rong Tong

  DOI：10.1021/jacs.7b01462

  日期：2017.5.3

  Poly(α-hydroxy acids) are important biodegradable polymers with wide applications. Attempts to synthesize them from O-carboxyanhydrides with pendant functional groups by various methods, including methods involving organocatalysts or organometallics, have been plagued by uncontrolled polymerization, including epimerization for some monomers, which hampers the preparation of stereoregular high-molecular-weight

  聚（α-羟基酸）是重要的可生物降解聚合物，应用广泛。通过各种方法（包括涉及有机催化剂或有机金属化合物的方法）从带有侧基官能团的 O-羧酸酐合成它们的尝试一直受到不受控制的聚合的困扰，包括某些单体的差向异构化，这阻碍了有规立构高分子量聚合物的制备。在此，我们描述了一种有效的协议，该协议将光氧化还原 Ni/Ir 催化与使用 Zn-醇盐进行有效的开环聚合相结合，从而合成具有预期分子量 (>140 kDa) 和窄分子量分布的全同立构聚酯（ Mw/Mn < 1.1)。