[Re(CO)3(3,5-dimethylpyrazole)2]Br | 215665-07-9

• 英文名称: [Re(CO)3(3,5-dimethylpyrazole)2]Br
• 英文别名: fac-[ReBr(CO)3(dmpzH)2]；fac-[ReBr(CO)3(3,5-dimethylpyrazole)2]；fac-[ReBr(CO)3(Hdmpz)2]
• CAS: 215665-07-9
• 化学式: C₁₃H₁₆BrN₄O₃Re
• 分子量: 542.406
• InChiKey: GPTIJQGXZDJJCK-UHFFFAOYSA-M

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：

  [Re(CO)3(3,5-dimethylpyrazole)2]Br 、 silver trifluoromethanesulfonate 以 四氢呋喃 为溶剂， 反应 2.0h， 以84%的产率得到fac-[Re(CO)₃(dmpzH)₂(OTf)]
  参考文献：
  名称：

  Pyrazolylamidino Ligands from Coupling of Acetonitrile and Pyrazoles: A Systematic Study

  摘要：

  (M)ixed pyrazole-acetonitrile complexes, both neutral fac-[ReBr(CO)3(NCMe)(pz*H)] (pz*H = pzH, pyrazole; dmpzH, 3,5-dimethylpyrazole; or indzH, indazole) and cationic fac-[Re(CO)(3)(NCMe)(pz*H)(2)]A (A = BF4, ClO4, or OTf), are described. Their role as the only starting products to obtain final pyrazolylamidino complexes fac-[ReBr(CO)(3)(NH-C(Me)pz*-eta N-2,N)] and fac-[Re(CO)(3)(pz*H)(NH-C(Me)pz*-eta N-2,N)]A, respectively, is examined. Other products involved in the processes, such as fac-[ReBr(CO)(3)(pz*H)(2)], fac-[Re(CO)(3)(NCMe)(NH-C(Me)pz*-eta N-2,N)]A, and fac-[Re(CO)(3)(pz*H)(2)(OTf)] are also described. Warming CD3CN solutions of fac-[Re(CO)(3)(NCMe)(pz*H)(2)]A at 40 degrees C gives cleanly the pyrazolylamidino complexes [Re(CO)(3)(pz*H)(NH-C(Me)pz*-eta N-2,N)]A as the only products, pointing to an intramolecular process. This is confirmed by carrying out reactions in the presence of one equivalent of a pyrazole different from that coordinated, which affords complexes where the pyrazolylamidino ligand contains only the pyrazole previously coordinated. When the reactions lead to an equilibrium mixture of the final and starting products, the reverse reaction gives the same equilibrium mixture, which indicates that the coupling reaction of pyrazoles and nitriles to obtain pyrazolylamidino ligands is a reversible intramolecular process. A systematic study of the possible factors which may affect the reaction gives the following results: (a) the yields of the direct reactions are higher for lower temperatures; (b) the tendency of the pyrazoles to give pyrazolylamidino complexes follows the sequence indzH > pzH > dmpzH; and (c) the reaction rates do not depend on the nature of the anion even when a large excess is added. The presence of a small amount of aqueous solution of NaOH catalyzes the reaction. Thus, addition of 0.5-1% of NaOH (aq) to solutions of fac-[ReBr(CO)(3)(NCMe)(pz*H)] (in CD3CN) or fac-[Re(CO)(3)(NCMe)(pz*H)(2)]A (in CD3CN, CD3NO2 or (CD3)(2)CO) allowed the syntheses of the corresponding pyrazolylamidino complexes [ReBr(CO)(3)(NH-C(Me)pz*-eta N-2,N)] or [Re(CO)(3)(pz*H)(NH-C(Me)pz*-eta N-2,N)]A with better yields, more rapidly, and in milder conditions.

  DOI：

  10.1021/ic5018054
• 作为产物：
  描述：

  3,5-二甲基吡唑 、 五羰基溴铼(I) 以 甲苯 为溶剂， 以85%的产率得到[Re(CO)3(3,5-dimethylpyrazole)2]Br
  参考文献：
  名称：

  Pyrazolato Metal Complexes: Synthesis, Characterization and X-ray Crystal Structures of Rhenium(I) Derivatives

  摘要：

  DOI：

  10.1002/(sici)1099-0682(199810)1998:10<1503::aid-ejic1503>3.0.co;2-0

文献信息

• Rhenium-Mediated Coupling of Acetonitrile and Pyrazoles. New Molecular Clefts for Anion Binding
  作者：Marta Arroyo、Daniel Miguel、Fernando Villafañe、Sonia Nieto、Julio Pérez、Lucía Riera

  DOI：10.1021/ic0607078

  日期：2006.8.1

  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.