[Re(neopentyl)2(neopentylidene)(neopentylydine)] | 850607-85-1

• 分子结构分类: 有机化合物
• 英文名称: [Re(neopentyl)2(neopentylidene)(neopentylydine)]
• 英文别名: syn-(tBuCH2)2Re(C-tBu)(CH-tBu)；anti-(tBuCH2)2Re(C-tBu)(CH-tBu)
• CAS: 850607-85-1；86823-35-0
• 化学式: C₂₀H₄₁Re
• 分子量: 467.753
• InChiKey: HHSUINCXMKUBEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.92
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  tetrakis[3,5-bis(trifluoromethyl)phenyl]boric acid bis(diethyl ether) complex 、 [Re(neopentyl)2(neopentylidene)(neopentylydine)] 以 乙醚 为溶剂， 以73%的产率得到
  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：

  、 氯化新戊烷基镁 以 四氢呋喃 、 乙醚 为溶剂， 以90%的产率得到[Re(neopentyl)2(neopentylidene)(neopentylydine)]
  参考文献：
  名称：

  Scott Edwards; Biondi, Linda Vollaro; Ziller, Joseph W., Organometallics, 1983, vol. 2, # 11, p. 1505 - 1513

  摘要：

  DOI：

文献信息

• Perhydrocarbyl Re^VII Complexes: Comparison of Molecular and Surface Complexes
  作者：Mathieu Chabanas、Anne Baudouin、Christophe Copéret、Jean-Marie Basset、Wayne Lukens、Anne Lesage、Sabine Hediger、Lyndon Emsley

  DOI：10.1021/ja020136s

  日期：2003.1.1

  solid-state NMR. This behavior parallels the reactivity of molecular Re complexes, and their respective 1H and 13C chemical shifts match those of the corresponding molecular analogues syn- and anti-2m and n. Finally, the grafting of 1 onto silica involves the reaction of both the alkyl and the alkylidene ligand with an equiprobability, leaving the alkylidyne as a spectator ligand. Noteworthy is the formation

  分子复合物 [Re(=CtBu)(=CHtBu)(CH2tBu)2] 1 与在 700 摄氏度下部分脱羟基的二氧化硅反应，得到 Syn-2，[(=SiO)Re(=CtBu)(=CHtBu)( CH2tBu)]，根据质量平衡分析、IR 和固态 NMR 光谱作为单一异构体。13C 标记的 2 上的 1D 和 2D 固态 NMR（HETCOR 和长程 HETCOR）使我们能够观察所有碳（包括未标记的碳）的化学位移并确定它们的分配。此外，EXAFS 数据与在相对较短的距离 (1.79 A) 处存在两个碳一致，这无法解卷积，但与亚烷基和亚烷基碳以及其他两个距离较远的第一个相邻碳的存在一致（ 2.01 A)、烷基碳和氧原子，Re 通过其连接到表面。而且，数据还表明在 Re 中心的配位球中存在 2.4 A 的二氧化硅表面的硅氧烷桥。热和光化学处理使我们能够观察到反异构体，它也被 1D 和 2D 固态 NMR
• A Highly Active Well-Defined Rhenium Heterogeneous Catalyst for Olefin Metathesis Prepared via Surface Organometallic Chemistry
  作者：Mathieu Chabanas、Anne Baudouin、Christophe Copéret、Jean-Marie Basset

  DOI：10.1021/ja000900f

  日期：2001.3.1