[(N,N-bis(2-C6F5-aminoethyl)methylamine)Re(O)(C(O)CH3)] | 1197376-09-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(N,N-bis(2-C6F5-aminoethyl)methylamine)Re(O)(C(O)CH3)]
• 英文别名: [(N,N-bis(2-C₆F₅-aminoethyl)methylamine)Re(O)(C(O)CH₃)]；ReOMe(MeN(CH2CH2NC6F5)2)
• CAS: 1197376-09-2
• 化学式: C₁₈H₁₄F₁₀N₃ORe
• 分子量: 664.52
• InChiKey: VNMNSNKYEWYYEE-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：

  一氧化碳 、 [(N,N-bis(2-C6F5-aminoethyl)methylamine)Re(O)(C(O)CH3)] 以 苯 为溶剂， 生成 [(N,N-bis(2-C₆F₅-aminoethyl)methylamine)Re(CO)(OAc)]
  参考文献：
  名称：

  氧铼配合物活化一氧化碳的机理

  摘要：

  铼 (V) 氧合络合物 [(DAAm)Re(O)(CH(3))] 对 CO 的活化 (1) [DAAm = N,N-双(2-芳基氨基乙基)甲胺；芳基 = C(6)F(5), Mes] 导致分离出醋酸铼 (III) 络合物 [(DAAm)Re(O(2)CCH(3))(CO)] (3)。通过实验探索了该反应的机理细节。分离出新型氧铼 (V) 酰基中间体 [(DAAm)Re(O)(C(O)CH(3))] (2)，并研究了其与 CO 的反应性。提出了一种前所未有的机制：CO 被金属氧配合物 1 活化并插入铼-甲基键中以产生酰基配合物 2，之后酰基配体随后迁移到金属氧配合物产生乙酸配合物 3。 X 射线报道了2和3的晶体结构。

  DOI：

  10.1021/ja205477w
• 作为产物：
  描述：

  以 not given 为溶剂， 生成 [(N,N-bis(2-C6F5-aminoethyl)methylamine)Re(O)(C(O)CH3)]
  参考文献：
  名称：

  氧铼配合物活化一氧化碳的机理

  摘要：

  铼 (V) 氧合络合物 [(DAAm)Re(O)(CH(3))] 对 CO 的活化 (1) [DAAm = N,N-双(2-芳基氨基乙基)甲胺；芳基 = C(6)F(5), Mes] 导致分离出醋酸铼 (III) 络合物 [(DAAm)Re(O(2)CCH(3))(CO)] (3)。通过实验探索了该反应的机理细节。分离出新型氧铼 (V) 酰基中间体 [(DAAm)Re(O)(C(O)CH(3))] (2)，并研究了其与 CO 的反应性。提出了一种前所未有的机制：CO 被金属氧配合物 1 活化并插入铼-甲基键中以产生酰基配合物 2，之后酰基配体随后迁移到金属氧配合物产生乙酸配合物 3。 X 射线报道了2和3的晶体结构。

  DOI：

  10.1021/ja205477w

文献信息

• Role of Low-Valent Rhenium Species in Catalytic Hydrosilylation Reactions with Oxorhenium Catalysts
  作者：Jessica L. Smeltz、Paul D. Boyle、Elon A. Ison

  DOI：10.1021/om300654q

  日期：2012.9.10

  The catalytic competency of a Re(III) complex has been demonstrated. In the presence of silane, oxorhenium(V) catalysts are deoxygenated to produce species that are significantly more active than the metal oxo precursors in hydrosilylation reactions. The results presented suggest that, in evaluating mechanisms for catalytic hydrosilylation reactions that involve high-valent metal oxo complexes, the activity of species that may be generated by deoxygenation of the metal with silane should also be systematically investigated as potential catalysts.
• Synthesis and Reactivity of Oxorhenium(V) Methyl, Benzyl, and Phenyl Complexes with CO: Implications for a Unique Mechanism for Migratory Insertion
  作者：Leanna K. Robbins、Cassandra P. Lilly、Jessica L. Smeltz、Paul D. Boyle、Elon A. Ison

  DOI：10.1021/acs.organomet.5b00177

  日期：2015.7.13

  The complexes [(DAAm)Re(O)(R)] [DAAm = N,N-bis(2-arylaminoethyl)methylamine; aryl = C6F5], 1, R = Me; 3a-d (R = benzyl, a; 4-methylbenzyl, b; 4-fluorobenzyl, 4-methoxybenzyl, d); and 4, R = Ph, were synthesized. CO insertion into the Re R bond in 1 and 3a d resulted in the formation of the acetyl complex, 2, and the (aryl)acetyl complexes, 5a-d respectively. The formation of 5a-d proceeded at a faster rate (7 h) than the formation of 2 (72 h) under the same conditions. No reaction was observed however: for the phenyl complex 4 with CO. Kinetics for CO insertion into the various Re R bonds were examined, and the experimental rate law was determined to be Rate = k(obs)[Re] [CO]. The activation parameters for CO insertion into 1 and 3a were determined to be AG double dagger(298 K) = 24(1): The enthalpy of activation Delta H double dagger was determined to be 9(1) and 10(3) kcal/mol for 1 and 3a, respectively, and the entropy of activation, Delta S double dagger, was -49(2) and -36(4) cal/mol-K. Computational studies (M06) are consistent with the hypothesis that the rate of CO insertion is dependent on the strength of the rhenium carbon bond: Thus, experimental and computational data suggest that the most likely mechanism for the insertion of CO into the Re-R bond in oxorhenium complexes is a direct-insertion mechanism.