Re(CH-t-Bu)(N-2,6-C6H3-i-Pr2)(O-2,6-C6H3(OMe)2)Cl2 | 134152-86-6

• 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: Re(CH-t-Bu)(N-2,6-C6H3-i-Pr2)(O-2,6-C6H3(OMe)2)Cl2
• CAS: 134152-86-6
• 化学式: C₂₅H₃₆Cl₂NO₃Re
• 分子量: 655.679
• InChiKey: XSUJUNCWPRWKAA-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  8.61
• 重原子数：
  32.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  40.05
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  2,6-二甲氧基苯酚 、 Re(C-tert-butyl)(N-2,6-C6H3-i-Pr2)Cl2(dimethoxyethane) 以 二氯甲烷 为溶剂， 以65%的产率得到Re(CH-t-Bu)(N-2,6-C6H3-i-Pr2)(O-2,6-C6H3(OMe)2)Cl2
  参考文献：
  名称：

  hen单亚胺基亚烷基络合物：合成，结构和路易斯酸共催化的烯烃复分解。

  摘要：

  Five-coordinate alkylidene complexes of the general type Re(CH-t-Bu)(NAr)(OAr')3 (NAr = N-2,6-C6H3-i-Pr2; OAr' = OC6F5 (1a), O-2,6-C6H3Cl2 (1b), OC6Cl5 (1c) can be prepared in high yield by treating [Re(C-t-Bu)(NHAr)Cl3]2 with 6 equiv of potassium phenoxide. Re(CH-t-Bu)(NAr)(O-2,6-C6H3Cl2)3 (P2(1)/c, a = 11.461 (3) angstrom, b = 32.86 (1) angstrom, c = 11.680 (2) angstrom, beta = 103.31 (2)degrees is essentially a square pyramid in which the alkylidene ligand occupies the apical position. Re(CH-t-Bu)(NAr)(OC6F5)3(THF) (2) is prepared in high yield from Re(C-t-Bu)(NHAr)Cl3(THF) and 3 equiv of KOC6F5. Re(CH-t-Bu)(NAr)(OC6F5)3(THF) (P1, a = 11.037 (7) angstrom, b = 17.66 (1) angstrom, c = 10.981 (6) angstrom, alpha = 90.28 (6)degrees, beta = 93.94 (6)degrees, gamma = 94.15 (5)degrees) is pseudooctahedral with THF bound at the coordination site trans to the alkylidene ligand. Re(CH-t-Bu)(NAr)(OAr')3 complexes do not react with terminal, internal, or strained cyclic olefins, possibly because an olefin can bind only to the site trans to the alkylidene ligand. Re(CH-t-Bu)(NAr)(OAr')3 complexes react with pyridine to form alkylidyne complexes of the type Re(C-t-Bu)(NAr)(OAr')2(py) (OAr' = O-2,6-C6H3Cl2 (3a), OC6Cl5 (3b). Alkylidene complexes of the type Re(CH-t-Bu)(NAr)(OAr')Cl2 (OAr' = O-2,6-C6H3Cl2 (4a), O-2,6-C6H3Me2 (4b), OAr (O-2,6-C6H3-i-Pr2), (4c), O-2,6-C6H3(OMe)2 (4d) can be prepared in high yield by treating Re(C-t-Bu)(NAr)(Cl2(DME) with 1 equiv of Ar'OH. NMR data suggest that Re(CH-t-Bu)(NAr)(OAr')Cl2 complexes are isostructural with Re(CH-t-Bu)(NAr)(OAr')3 complexes. Re(CH-t-Bu)(NAr)(OAr')Cl2 complexes also do not readily react with terminal, internal, or strained cyclic olefins. However, addition of GaBr3 to Re(CH-t-Bu)(NAr)(OAr')Cl2 (OAr' = O-2,6-C6H3Cl2, O-2,6-C6H3Me2, OAr) yields highly active catalysts that metathesize trans-3-heptene at a rate of approximately 1000 turnover min-1. In some cases propagating alkylidene species can be observed by NMR spectroscopy. Re(CH-t-Bu)-(NAr)(OAr')Cl2 complexes react with pyridine to produce complexes of the type Re(C-t-Bu)(NAr)Cl2(py)2.

  DOI：

  10.1021/om00052a034