tris(2,6-diisopropylphenylimido)rhenium chloride | 135228-54-5

• 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: tris(2,6-diisopropylphenylimido)rhenium chloride
• 英文别名: Re(N(2,6-diisopropylphenyl)3)Cl
• CAS: 135228-54-5
• 化学式: C₃₆H₅₁ClN₃Re
• 分子量: 747.481
• InChiKey: KBEZUAAQRCJFSW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  13.58
• 重原子数：
  41.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.08
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  tris(2,6-diisopropylphenylimido)rhenium chloride 在 sodium amalgam 、 dimethylammonium triflate 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Synthesis and reactivity of a series of analogous rhenium tris(imido), bis(imido) alkyne, and imido bis(alkyne) complexes

  摘要：

  A reaction between Re2O7, ArNH2 (Ar = 2,6-C6H3-i-Pr2), NEt3, and Me3SiCl yields Re(NAr)3Cl. Reduction of Re(NAr)3Cl in THF by 1 equiv of sodium amalgam gives Hg[Re(NAr)s]2 in ca. 50% yield. An X-ray study showed Hg[Re(NAr)3]2 to be composed of molecular units of (ArN)3Re-Hg-Re(NAr)3 having a linear Re-Hg-Re bond and nearly trigonal planar staggered Re(NAr)3 units. Reduction of either Hg[Re(NAr)3]2 or Re(NAr)3Cl by 2 equiv of sodium amalgam in THF affords Na(THF)2Re(NAr)3 in high yield. An X-ray structure of [N(PPh3)2][Re(NAr)3] showed that the [Re(NAr)3]- ion is a trigonal planar species in which the Re-N-C angles all are essentially linear. Compounds that contain the [Re(NAr)3]- ion can be alkylated to give compounds of the type Re(NAr)3R and protonated to give Re(NAr)3H. Reactions between Re(NAr)3H and pi-acceptor ligands yield pseudotetrahedral compounds of the type Re(NAr)2(NHAr)(eta2-L) [L = C2H2, C2Me2, OCHCMe3, C2H4, or norbornene]. Addition of 2 equiv of pyHCl to Re(NAr)3Cl yields Re(NAr)2Cl3(PY). Reduction of Re(NAr)2Cl3(PY) with sodium amalgam in THF in the presence of MeC=CMe or NpC=CNp (Np = neopentyl) yields complexes of the type Re(NAr)2(eta2-C2R2)Cl. Reduction of Re(NAr)2(eta2-C2NP2)Cl by 1 equiv of sodium amalgam yields Hg[Re(NAr)2(eta2-C2NP2)]2, while reduction by 2 equiv of sodium amalgam yields pentane-soluble Na(THF)2Re(NAr)2(eta2-C2Np2). Na(THF)2Re(NAr)2(eta2-C2Np2)reacts with MeI or ClCH2-2,4,6-C6H2Me3 to yield Re(NAr)2(eta2-C2NP2)R or with [Et2NH2][OTf] in THF to give Re(NAr)2(eta2-C2NP2)H. Addition of excess PMe2Ph to Re(NAr)2(eta2-C2NP2)H yields Re(NAr)2(PMe2Ph)2H. Addition of 4 equiv of pyridinium chloride in a 1:5 mixture of THF and pyridine to Na(THF)2Re(NAr)3 affords Re(NAr)Cl3(PY)2 in high yield. Re(NAr)Cl3(PY)2 is reduced by excess Zn dust in the presence of 2 equiv of dineopentylacetylene in refluxing THF to afford Re(NAr)(eta2-C2NP2)2Cl. Reduction of Re(NAr)(eta2-C2NP2)2Cl by 1 or 2 equiv of sodium amalgam in THF yields Hg[Re(NAr)(eta2-C2NP2)2]2 or Na(THF)2Re(NAr)(eta2-C2NP2)2, respectively. The molecular structure of Na(THF)2Re(NAr)(eta2-C2Np2)2 shows that [Na(THF)2]+ is bound to the imido nitrogen atom (2.464(9) angstrom), not to rhenium (Re-Na = 3.17 angstrom), and the coordination about the rhenium center is distorted from the pseudotrigonal planar geometry expected for [Re(NAr)(eta2-C2NP2)2]-. Na(THF)2Re(NAr)(eta2-C2NP2)2 is alkylated smoothly by MeI or ClCH2-2,4,6-C6H2Me3 to afford Re(NAr)(eta2-C2NP2)2R, while addition of [Et2NH2][OTf] yields pale yellow Re(NAr)(eta2-C2NP2)2H. Cyclic voltammograms (200 mV s-1) were obtained for the chloride derivatives and sodium salts of the tris-, bis-, and mono(imido) complexes in a solution of 0.5 M[NBu4][PF6] in THF. Extended Huckel calculations on [Re(NH)3]-, [Re(NH)2(C2H2)]-, and Re(NH)(C2H2)2]- all clearly show that a 20-electron count on the metal is avoided by filling a ligand-centered nonbonding orbital.

  DOI：

  10.1021/om00028a032
• 作为产物：
  描述：

  tris((2,6-diisopropylphenyl)imino)rhenium(VII) hydride 在 CCl₄ 作用下， 以 not given 为溶剂， 生成 tris(2,6-diisopropylphenylimido)rhenium chloride
  参考文献：
  名称：

  Williams, Darryl S.; Anhaus, Jens T.; Schofield, Mark. H., Journal of the American Chemical Society, 1991, vol. 113, p. 5480 - 5481

  摘要：

  DOI：

文献信息

• Cheng, Jack Y. K.; Cheung, Kung-Kai; Chan, Michael C. W., Inorganica Chimica Acta, 1998, vol. 272, # 1-2, p. 176 - 187
  作者：Cheng, Jack Y. K.、Cheung, Kung-Kai、Chan, Michael C. W.、Wong, Kwok-Yin、Che, Chi-Ming

  DOI：——

  日期：——
• Yatsunyk, Liliya A.; Walker, F. Ann, Inorganic Chemistry, 2004, vol. 43, # 14, p. 4341 - 4352
  作者：Yatsunyk, Liliya A.、Walker, F. Ann

  DOI：——

  日期：——