fac-[Re(acetonitrile)(3,5-dimethylpyrazole)2(CO)3][B(Ar')4] | 908117-68-0

• 英文名称: fac-[Re(acetonitrile)(3,5-dimethylpyrazole)2(CO)3][B(Ar')4]
• 英文别名: fac-[Re(acetonitrile)(Hdmpz)2(CO)3][B(Ar')4]
• CAS: 908117-68-0
• 化学式: C₁₅H₁₉N₅O₃Re*C₃₂H₁₂BF₂₄
• 分子量: 1366.77
• InChiKey: WRSQDBFZIMRAMF-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：

  fac-[Re(acetonitrile)(3,5-dimethylpyrazole)2(CO)3][B(Ar')4] 以 二氯甲烷 、 乙腈 为溶剂， 以78%的产率得到fac-[Re(Hdmpz)(CO)3(HN=C(CH3)dmpz-κ2N,N)][B(Ar')4]
  参考文献：
  名称：

  Rhenium-Mediated Coupling of Acetonitrile and Pyrazoles. New Molecular Clefts for Anion Binding

  摘要：

  The reaction of fac-[ReBr(CO)(3)(NCMe)(2)] (1) with either pyrazole (Hpz) or 3,5-dimethylpyrazole (Hdmpz) in a 1:2 Re/pyrazole ratio affords the known complexes fac-[ReBr(CO)(3)(Hpz)(2)] (2) and [ReBr(CO)(3)(Hdmpz)(2)] (3). Using a 1:1 ratio, MeCN as solvent, and longer reaction times led to a mixture in which the major components are the pyrazolylamidino complexes fac-[ReBr(CO)(3)(HN=C(CH3)pz-kappa N-2,N)] (4) and fac-[ReBr(CO)(3)(HN = C(CH3)dmpz-kappa N-2,N)] (5). The complexes fac-[ReBr(CO)(3)(Hpz)(NCMe)] (6) and fac-[ReBr(CO)(3)(Hdmpz)(NCMe)] (7) (along with 2 and 3) were found to be minor components of these reactions. Analogous reactions of fac-[Re(OClO3)(CO)(3)(NCMe)(2)] yielded fac-[Re(NCCH3)(CO)(3)(HN=C(CH3)pz-kappa N-2,N)]ClO4 (8), fac-[Re(NCCH3)(CO)(3)(HN=C(CH3)dmpz-k(2)N,N)]ClO4 (9), fac-[Re(Hpz)(CO)(3)(HN=C(CH3)pz-kappa N-2,N)]ClO4 (10), and fac-[Re(Hdmpz)(CO)(3)(HN=C(CH3)dmpz-kappa N-2,N)]ClO4 (11). The X-ray structure of 11 showed the perchlorate anion to be hydrogen-bonded by the N-H groups of the pyrazole and pyrazolylamidino ligands. The behavior of the compound fac-[Re(Hdmpz)(CO)(3)(HN=C(CH3)dmpz-kappa N-2,N)]BAr'(4) (13) (synthesized by reaction of [ReBr(CO)(3)(Hdmpz)(2)] (3) with (i) AgOTf and (ii) NaBAr'(4)/MeCN) as an anion receptor has been studied in CD3CN solution. In addition, the structure of the supramolecular adduct fac-[Re(CO)(3)(Hdmpz)(HN=C(CH3)dmpz-kappa N-2,N)]center dot Cl (14), featuring chloride binding by the two N-H groups, was determined by X-ray diffraction.

  DOI：

  10.1021/ic0607078
• 作为产物：
  描述：

  [Re(CO)3(3,5-dimethylpyrazole)2]Br 、 四(3,5-二(三氟甲基)苯基)硼酸钠 、 乙腈 在 AgO₃SCF₃ 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 以72%的产率得到fac-[Re(acetonitrile)(3,5-dimethylpyrazole)2(CO)3][B(Ar')4]
  参考文献：
  名称：

  Rhenium-Mediated Coupling of Acetonitrile and Pyrazoles. New Molecular Clefts for Anion Binding

  摘要：

  The reaction of fac-[ReBr(CO)(3)(NCMe)(2)] (1) with either pyrazole (Hpz) or 3,5-dimethylpyrazole (Hdmpz) in a 1:2 Re/pyrazole ratio affords the known complexes fac-[ReBr(CO)(3)(Hpz)(2)] (2) and [ReBr(CO)(3)(Hdmpz)(2)] (3). Using a 1:1 ratio, MeCN as solvent, and longer reaction times led to a mixture in which the major components are the pyrazolylamidino complexes fac-[ReBr(CO)(3)(HN=C(CH3)pz-kappa N-2,N)] (4) and fac-[ReBr(CO)(3)(HN = C(CH3)dmpz-kappa N-2,N)] (5). The complexes fac-[ReBr(CO)(3)(Hpz)(NCMe)] (6) and fac-[ReBr(CO)(3)(Hdmpz)(NCMe)] (7) (along with 2 and 3) were found to be minor components of these reactions. Analogous reactions of fac-[Re(OClO3)(CO)(3)(NCMe)(2)] yielded fac-[Re(NCCH3)(CO)(3)(HN=C(CH3)pz-kappa N-2,N)]ClO4 (8), fac-[Re(NCCH3)(CO)(3)(HN=C(CH3)dmpz-k(2)N,N)]ClO4 (9), fac-[Re(Hpz)(CO)(3)(HN=C(CH3)pz-kappa N-2,N)]ClO4 (10), and fac-[Re(Hdmpz)(CO)(3)(HN=C(CH3)dmpz-kappa N-2,N)]ClO4 (11). The X-ray structure of 11 showed the perchlorate anion to be hydrogen-bonded by the N-H groups of the pyrazole and pyrazolylamidino ligands. The behavior of the compound fac-[Re(Hdmpz)(CO)(3)(HN=C(CH3)dmpz-kappa N-2,N)]BAr'(4) (13) (synthesized by reaction of [ReBr(CO)(3)(Hdmpz)(2)] (3) with (i) AgOTf and (ii) NaBAr'(4)/MeCN) as an anion receptor has been studied in CD3CN solution. In addition, the structure of the supramolecular adduct fac-[Re(CO)(3)(Hdmpz)(HN=C(CH3)dmpz-kappa N-2,N)]center dot Cl (14), featuring chloride binding by the two N-H groups, was determined by X-ray diffraction.

  DOI：

  10.1021/ic0607078