(2,2-dimethylpropylidyne)trineopentyl(((trifluoromethyl)sulfonyl)oxy)rhenium | 86834-32-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (2,2-dimethylpropylidyne)trineopentyl(((trifluoromethyl)sulfonyl)oxy)rhenium
• CAS: 86834-32-4
• 化学式: C₂₁H₄₂F₃O₃ReS
• 分子量: 617.831
• InChiKey: FUENYWMHNRBFGR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.86
• 重原子数：
  29.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  氘代四氢呋喃 、 (2,2-dimethylpropylidyne)trineopentyl(((trifluoromethyl)sulfonyl)oxy)rhenium 以 氘代甲醇 为溶剂， 生成
  参考文献：
  名称：

  R的烷基，亚炔基和亚炔基络合物

  摘要：

  The reaction of Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(2) with triflic acid, pentafluorophenol, HBF4 . OEt(2), or [H(OEt(2))(2)](+)[BAr4F](-) (Ar-F = 3,5-C6H3(CF3)(2)) yields complexes of the general formula Re(C-t-Bu)(CH2-t-Bu)(3)X (X = OTf, OC6F5, BF4, BAr4F) in 60-80% yield. Re(C-t-Bu)(CH2-t-Bu)(3)X reacts with coordinating ligands L (L = py, CH3CN, CD3OD, THF) to form neopentane and Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(L)(n)X (n = 1-3). The reaction of Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(py)(2)(OTf) with NaC5H5, NaL(OEt) (L(OEt) = [CpCo(PO(OEt)(2))(3)], or NaHBpz(3) in THF yields Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(eta(5)-C5H5), Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(L(OEt)), or Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(HBpz(3)), respectively, while the reaction between Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(py)(2)(OTf) and 1,4,7-trithiacyclononane produces colorless [Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(eta(3)-S3C6H12)](+)[OTf](-) in 96% yield. Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(L) (L = Cp, L(OEt)) and [Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(eta(3)-S3C6H12)](+)[OTf](-) react with triflic acid to form Re(C-t-Bu)(CH-t-Bu)(L)(OTf) or [Re(C-t-Bu)(CH-t-Bu)(OTf)-(eta(3)-S3C6H12)](+)[OTf](-), respectively. A similar reaction between Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(L(OEt)) and [H(OEt(2))(2)](+)[BAr4F](-) in ether produces [Re(C-t-Bu)(CH-t-Bu)(OEt(2))(L(OEt))](+)[BAr4F](-). Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(py)(2)(OTf) reacts with H2C=CHR (R = OCH2CH3, C6H5) to yield neohexene and Re(C-t-Bu)(CHR)(CH2-t-Bu)(py)(2)(OTf) complexes. Re(C-t-Bu)(CH-t-Bu)-(CH2-t-Bu)(py)(2)(OTf) reacts with ethylene to form the unstable methylidene complex, Re(C-t-Bu)(CH2)(CH2-t-Bu)(py)(2)(OTf), which can be trapped upon addition of bpy to yield red Re(C-t-Bu)(CH2)(CH2-t-Bu)(bpy)(OTf). Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(py)(2)(OTf) reacts with excess ethylene to form colorless Re(C-t-Bu)[(CH2)(3)-t-Bu](C(2)H4)(py)(2)(OTf) in 85% yield. Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(CH3CN)(OTf) metathesizes 100 equiv of cis-2-pentene in less than 5 min, but the catalyst is not long-lived.

  DOI：

  10.1021/om00004a047
• 作为产物：
  描述：

  [Re(neopentyl)2(neopentylidene)(neopentylydine)] 、 三氟甲磺酸 以 乙醚 为溶剂， 以71%的产率得到(2,2-dimethylpropylidyne)trineopentyl(((trifluoromethyl)sulfonyl)oxy)rhenium
  参考文献：
  名称：

  R的烷基，亚炔基和亚炔基络合物

  摘要：

  The reaction of Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(2) with triflic acid, pentafluorophenol, HBF4 . OEt(2), or [H(OEt(2))(2)](+)[BAr4F](-) (Ar-F = 3,5-C6H3(CF3)(2)) yields complexes of the general formula Re(C-t-Bu)(CH2-t-Bu)(3)X (X = OTf, OC6F5, BF4, BAr4F) in 60-80% yield. Re(C-t-Bu)(CH2-t-Bu)(3)X reacts with coordinating ligands L (L = py, CH3CN, CD3OD, THF) to form neopentane and Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(L)(n)X (n = 1-3). The reaction of Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(py)(2)(OTf) with NaC5H5, NaL(OEt) (L(OEt) = [CpCo(PO(OEt)(2))(3)], or NaHBpz(3) in THF yields Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(eta(5)-C5H5), Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(L(OEt)), or Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(HBpz(3)), respectively, while the reaction between Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(py)(2)(OTf) and 1,4,7-trithiacyclononane produces colorless [Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(eta(3)-S3C6H12)](+)[OTf](-) in 96% yield. Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(L) (L = Cp, L(OEt)) and [Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(eta(3)-S3C6H12)](+)[OTf](-) react with triflic acid to form Re(C-t-Bu)(CH-t-Bu)(L)(OTf) or [Re(C-t-Bu)(CH-t-Bu)(OTf)-(eta(3)-S3C6H12)](+)[OTf](-), respectively. A similar reaction between Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(L(OEt)) and [H(OEt(2))(2)](+)[BAr4F](-) in ether produces [Re(C-t-Bu)(CH-t-Bu)(OEt(2))(L(OEt))](+)[BAr4F](-). Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(py)(2)(OTf) reacts with H2C=CHR (R = OCH2CH3, C6H5) to yield neohexene and Re(C-t-Bu)(CHR)(CH2-t-Bu)(py)(2)(OTf) complexes. Re(C-t-Bu)(CH-t-Bu)-(CH2-t-Bu)(py)(2)(OTf) reacts with ethylene to form the unstable methylidene complex, Re(C-t-Bu)(CH2)(CH2-t-Bu)(py)(2)(OTf), which can be trapped upon addition of bpy to yield red Re(C-t-Bu)(CH2)(CH2-t-Bu)(bpy)(OTf). Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(py)(2)(OTf) reacts with excess ethylene to form colorless Re(C-t-Bu)[(CH2)(3)-t-Bu](C(2)H4)(py)(2)(OTf) in 85% yield. Re(C-t-Bu)(CH-t-Bu)(CH2-t-Bu)(CH3CN)(OTf) metathesizes 100 equiv of cis-2-pentene in less than 5 min, but the catalyst is not long-lived.

  DOI：

  10.1021/om00004a047

文献信息

• Scott Edwards; Biondi, Linda Vollaro; Ziller, Joseph W., Organometallics, 1983, vol. 2, # 11, p. 1505 - 1513
  作者：Scott Edwards、Biondi, Linda Vollaro、Ziller, Joseph W.、Churchill, Melvyn Rowen、Schrock, Richard R.

  DOI：——

  日期：——