(dihydrobis(pyrazol-1-yl)borate)Rh(CO)2 | 33058-09-2

• 英文名称: (dihydrobis(pyrazol-1-yl)borate)Rh(CO)2
• 英文别名: Rh(dihydrobis(pyrazolyl)borate)(CO)2
• CAS: 33058-09-2
• 化学式: C₈H₈BN₄O₂Rh
• 分子量: 305.894
• InChiKey: OABRRHNQGLFBBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (dihydrobis(pyrazol-1-yl)borate)Rh(CO)2 、 三苯基膦 以 二氯甲烷 为溶剂， 生成 (dihydrobis(pyrazol-1-yl)borate)Rh(CO)(PPh3)
  参考文献：
  名称：

  Photochemical C−H Bond Activation Reactivity of (HBPz‘₃)Rh(CO)₂ (Pz‘ = 3,5-Dimethylpyrazolyl) in Alkane Solutions

  摘要：

  The intermolecular C-H bond activation photochemistry of (HBPz'(3))Rh(CO)(2) (Pz' = 3,5-dimethylpyrazolyl) has been investigated in various alkane solutions at 293 K. Excitations have been performed at 313-458 nm into the lowest energy absorption band of this complex, and the reactions have been monitored throughout photolysis by in situ UV-visible and FTIR spectroscopy. The spectral results reveal that the photochemistry is exceptionally clean and that the reagent complex can be completely converted to the corresponding (HBPz'(3))Rh(CO)(R)H photoproduct at each of the irradiation wavelengths. Absolute photochemical quantum efficiencies (phi(CH)) for these reactions have been determined and illustrate that the intermolecular C-H bond activation process is strongly wavelength dependent. Very effective conversion (phi(CH) = 0.31-0.34) is attained upon near-UV excitation at 313 or 366 nm. In contrast, inefficient conversion (phi(CH) = 0.010-0.011) is observed on visible excitation at 458 nn. The differences in reactivities are interpreted on a photophysical scheme in which the irradiations produce two ligand field (LF) electronically excited states with different primary photoproducts. The thermal chemistry of (HBPz'(3))Rh(CO)(2) in room-temperature solution is characterized as involving facile eta(3) <-> eta(2) ligand interconversions. Accordingly, the complex is readily protonated to form [(eta(2)-HBPz'(2)(Pz'H))Rh(CO)(2)]BF4, and when PPh(3) is added to a solution of (HBPz'(3))Rh(CO)(2), the ligand substitution product, (HBPz'(3))Rh(CO)PPh(3), is formed immediately. In contrast, there is no evidence of thermal ligand scavenging of (HBPz'(3))Rh(CO)(2) by pyridine and upon irradiation in pyridine solutions the photochemistry is dominated by the C-H activation reaction of the hydrocarbon solvent. In triethylsilane solutions the observed spectral changes reveal that intermolecular Si-H bond activation takes place readily on excitation of (HBPz'(3))Rh(CO)(2) at 366 nm. The thermal chemistry of the analogous square planar complex (H(2)BPz(2))Rh(CO)(2) has been investigated, and the complex has been found to be reactive toward PPh(3) and not R-H in room-temperature solution under dark conditions. These experimental observations imply that the long-wavelength (458 nm) photochemistry and thermal chemistry of (HBPz'(3))Rh(CO)(2) are associated with a (eta(2)-HBPz'(3))Rh(CO)(2) intermediate that is unable to facilitate hydrocarbon C-H bond activation. Importantly, the observed results also suggest that the short-wavelength (313, 366 nm) photochemistry proceeds via an extremely short-lived monocarbonyl (HBPz'(3))Rh(CO) complex that undergoes efficient C-H activation.

  DOI：

  10.1021/ic951199x
• 作为产物：
  描述：

  (dihydridobis(1-pyrazolyl)borato)(1,5-cyclooctadiene)rhodium(I) 在 CO 作用下， 以 苯 为溶剂， 以70%的产率得到(dihydrobis(pyrazol-1-yl)borate)Rh(CO)2
  参考文献：
  名称：

  Cocivera, Michael; Desmond, Timothy J.; Ferguson, George, Organometallics, 1982, vol. 1, # 9, p. 1125 - 1132

  摘要：

  DOI：

文献信息

• Synthesis and characterisation of rhodium(I) complexes containing the dihydrobis(pyrazolyl)borate ligands [H2B(pz′)2]. The X-ray structures of Bp*Rh(C2H4)2 and BpRh(PPh3)2 (Bp = H2B(pz)2; Bp* = H2B(3,5-Me2-pz)2
  作者：M. Jesús Baena、Manuel L. Reyes、Luis Rey、Ernesto Carmona、M. Carmen Nicasio、Pedro J. Pérez、Enrique Gutiérrez、Angeles Monge

  DOI：10.1016/s0020-1693(97)06146-x

  日期：1998.5

  the disubstituted sixteen electron compounds Bp*Rh(L)2. The ethylene groups in 1* and 1 can also be replaced by carbon monoxide and tert-butyl isocyanide, affording the complexes Bp′Rh(L)2 (L - CO, CN1Bu). The solid state structures of the compounds Bp*Rh(C2H4)2 (1*) and BpRh(PPh3)2 (9) have been determined by X-ray diffraction studies. Crystals of 1* are monoclinic, space group P21/c, with a = 15

  描述了双（乙烯）配合物Bp'Rh（C 2 H 4）2（Bp' -Bp *; 1 *; Bp'-Bp，1）的形成和某些取代化学。1 *与1当量的反应 N-供体配体或单齿膦（L）的合成导致通式为Bp * Rh（C 2 H 4）（L）的化合物的分离。添加过量的胺会产生18个电子络合物Bp * Rh（C 2 H 4）（L）2，而在PR 3配体的情况下，给体的第二个等价物会给出双取代的16个电子化合物Bp * Rh（L） ）2。1 *和1中的亚乙基也可以被一氧化碳和异丁基叔丁基取代，得到配合物Bp'Rh（L）2（L-CO，CN 1 Bu）。已经通过X射线衍射研究确定了化合物Bp * Rh（C 2 H 4）2（1 *）和BpRh（PPh 3）2（9）的固态结构。1 *晶体是单斜晶体，空间群P 2 1 / c，a = 15.129（3），b = 17.501（3），c＝ 13.425（8），β＝ 111