Ni(0)(tBuC6H2(OMe)(C6H4PiPr2)2) | 1365932-99-5

• 英文名称: Ni(0)(tBuC6H2(OMe)(C6H4PiPr2)2)
• CAS: 1365932-99-5
• 化学式: C₃₅H₅₀NiOP₂
• 分子量: 607.419
• InChiKey: CREDGUUDQZTISL-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：

  Ni(0)(tBuC6H2(OMe)(C6H4PiPr2)2) 以 not given 为溶剂， 生成 (tBuC6H3(C6H4PiPr2)2)Ni(CO)
  参考文献：
  名称：

  芳醚 C-O 键的镍介导氢解：氢的来源是什么？

  摘要：

  用（二膦）芳基甲基醚对镍对芳基醚进行氢解的机理研究。分离出含有与芳基-O 键相邻的 Ni-芳烃相互作用的 Ni(0) 配合物。加热导致芳基-O 键活化并生成芳基甲醇镍络合物。该物种的正式β-H消除产生芳基氢化镍，其可以在甲醛存在下进行还原消除以生成Ni(0)的一氧化碳加合物。报道的配合物描绘了镍催化芳醚氢解的合理机制。对先前报道的使用同位素标记底物的催化系统的研究与化学计量系统中提出的机制一致，涉及从醇镍中消除 β-H，而不是通过 H(2) 裂解 Ni-O 键。

  DOI：

  10.1021/ja300326t
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 1,3-bis(2′-diisopropylphosphinophenyl)-5-tert-butyl-2-methoxybenzene 以 四氢呋喃 为溶剂， 生成 Ni(0)(tBuC6H2(OMe)(C6H4PiPr2)2)
  参考文献：
  名称：

  芳醚 C-O 键的镍介导氢解：氢的来源是什么？

  摘要：

  用（二膦）芳基甲基醚对镍对芳基醚进行氢解的机理研究。分离出含有与芳基-O 键相邻的 Ni-芳烃相互作用的 Ni(0) 配合物。加热导致芳基-O 键活化并生成芳基甲醇镍络合物。该物种的正式β-H消除产生芳基氢化镍，其可以在甲醛存在下进行还原消除以生成Ni(0)的一氧化碳加合物。报道的配合物描绘了镍催化芳醚氢解的合理机制。对先前报道的使用同位素标记底物的催化系统的研究与化学计量系统中提出的机制一致，涉及从醇镍中消除 β-H，而不是通过 H(2) 裂解 Ni-O 键。

  DOI：

  10.1021/ja300326t

文献信息

• Lewis Acid Accelerated Aryl Ether Bond Cleavage with Nickel: Orders of Magnitude Rate Enhancement Using AlMe₃
  作者：Paul Kelley、Guy A. Edouard、Sibo Lin、Theodor Agapie

  DOI：10.1002/chem.201604160

  日期：2016.11.21

  Study of the kinetics of intramolecular aryl ether C−O bond cleavage by Ni was facilitated by access to a family of metal complexes supported by diphosphines with pendant aryl‐methyl ethers. The nature of the aryl substituents was found to have little effect on the rate of cleavage. In contrast, soluble Lewis acidic additives accelerate the aryl ether cleavage dramatically. The effect of AlMe3 was studied

  镍对分子内芳基醚C-O键断裂动力学的研究是通过获得由双膦与侧基芳基甲基醚支持的金属配合物来进行的。发现芳基取代基的性质对裂解速率几乎没有影响。相反，可溶的路易斯酸性添加剂显着加速了芳基醚的裂解。详细研究了AlMe 3的作用，并显示出速率增加了几个数量级。低温NMR光谱研究表明，醚与Al的定量配位。从路易斯酸结合的前体中，用于醚裂解的活化参数明显较低。这些发现为更温和的催化剂设计提供了机械基础，以激活强键。
• Aryl Ether Cleavage by Group 9 and 10 Transition Metals: Stoichiometric Studies of Selectivity and Mechanism
  作者：Guy A. Edouard、Paul Kelley、David E. Herbert、Theodor Agapie

  DOI：10.1021/acs.organomet.5b00710

  日期：2015.11.9

  The reactivity of terphenyl diphosphines bearing aryl methyl ether or aryl-aryl ether moieties with M-0 (M = Ni, Pd, Pt), M'(I) (M' = Co, Rh, Ir), or M-II centers was investigated to gain mechanistic insight into intramolecular aryl ether bond cleavage in structurally related metal complexes. Rh-I converts the aryl methyl ether moiety to an aryl C-H bond. This is similar to reactivity previously observed at Ni-0 that involves C-O oxidative addition, beta-H elimination liberating CH2O, reductive elimination of an aryl C-H bond, and decarbonylation of CH2O. Ir-I leads to unselective aryl and alkyl C-O bond activation. In the presence of excess CO, Rh-I and Ir-I display a shift in selectivity and reactivity and cleave the alkyl C-O bond. Co-I does not perform C-O cleavage. Alkyl C-O bond activation was observed with M-II-halide complexes with loss of MeCl via a Lewis acid-base mechanism. Pd-0 and Pt-0 cleave selectively the O-Me bond via oxidative addition. With a diaryl ether moiety, Pd-0 and Pt-0 are found to be capable of performing aryl C-O bond activation. Various levels of interactions between the central arene and the metal center were observed, and these were correlated with trends in bond activation. Overall, selective cleavage of the stronger aryl ether C-O bond was observed only with Ni-0 and Rh-I. Pd-0 and Pt-0 can perform aryl ether C-O cleavage, but if available, they will cleave the weaker O-Me bond. This study provides insight into the relative reactivity of group 9 and 10 metal centers with aryl ether bonds and suggests future directions for designing systems for metal-catalyzed cleavage of ether C-O bonds in synthetic methodology as well as lignin deoxygenation.