| 157045-54-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• CAS: 157045-54-0
• 化学式: CF₃O₃S*C₁₀H₂₆N₃Pd
• 分子量: 443.827
• InChiKey: HJNFQKLOBDACOD-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：

  、 一氧化碳 以 丙酮 为溶剂， 以93%的产率得到(acetyl)(N,N,N',N'',N''-pentamethyldiethylenetriamine)palladium trifluoromethanesulfonate
  参考文献：
  名称：

  一氧化碳插入带有三齿氮供体配体的阳离子单有机钯（II）配合物中的插入机理的高压NMR和从头算计算研究

  摘要：

  A number of methyl and arylpalladium(II) cations bearing tridentate nitrogen-donor ligands has been prepared, and their reactivity in the insertion of carbon monoxide has been studied. The resulting acetyl and aroylpalladium complexes of the ligands N-(2-picolyl)N,N',N'-trimethylethylenediamine (pico) and N,N,N',N '' N ''-pentamethyldiethylenetriamine (pmdeta) were isolated and characterized. In the case of the 4-nitrophenylpalladium and 2,4,6-trimethylphenylpalladium pico- and pmdeta complexes, no carbonylation products could be isolated. In these cases, either the equilibrium of the carbonylation reaction did not lie fully to the side of the insertion product even at 10 atm of CO or the insertion product decarbonylated upon attempted isolation. The methylpalladium complex of the 2,6-bis[(dimethylamino)methyl]pyridine (NN'N) ligand reacted quantitatively with CO in CD3-COCD3 to give acetic anhydride, palladium metal, and the protonated ligand; a mechanism for the anhydride formation is proposed. With the exception of the 1-naphthoyl derivative, the aroyl complexes of the NN'N ligand could not be isolated due to decarbonylation upon attempted isolation. Most of the unstable insertion products could, however, be characterized by IR and high-pressure NMR. Crystals of the 1-naphthoylpalladium complex with the NN'N ligand were obtained from acetone/pentane under a CO atmosphere. This complex is the first example of an aroylpalladium(II) cation. Two reaction pathways for the carbonyl insertion reaction, i.e., dissociative and associative, have been evaluated using H-1 NMR studies and ab initio calculations. The insertion reaction at 10 atm of CO pressure in CD3-COCD3 is complete within 2.5 min for most complexes, with the exception of those bearing strongly electron-withdrawing para substituents (e.g., NO2) or sterically demanding ortho substituents (e.g., 2,4,6-trimethyl) on the aryl ring. Ab initio calculations at the RHF, MP2//SCF, and CAS-SCF/CI levels on the cationic model system [Pd(CH3)(NH3)(3)](+) + CO and the neutral system [Pd(CH3)(2)(NH3)(2)] + CO show that the carbonylation reaction follows a hybrid pathway, i.e., a concerted replacement of NH3 by CO followed by migratory insertion of CO into the Pd-C bond instead of a purely dissociative or associative mechanism. For both the neutral and the cationic systems the rate-determining step is the migratory insertion. The insertion process is enhanced by coordination of the dissociated amine and is slightly more favorable in the neutral system. Together with the low-energy replacement of NH3 by CO, this implies that in both systems the rate of carbonyl insertion should be independent of the applied CO pressure.

  DOI：

  10.1021/om00012a032
• 作为产物：
  描述：

  五甲基二乙烯三胺 、 (N,N,N',N'-tetramethylethylenediamine)Pd(CH3)(acetonitrile) trifluoromethanesulfonate 以 丙酮 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Synthesis and Structural Studies of Ionic Monoorganopalladium(II) Complexes with Tridentate Nitrogen-Donor Ligands

  摘要：

  Ionic palladium(II) complexes of the types [PdCl(N-N'-N'')]Cl and [PdR(N-N'-N'')]OTf, with R = Me or aryl, N-N'-N'' = tridentate nitrogen donor ligand, and OTf = trifluoromethane-sulfonate (triflate), have been prepared. The tridentate nitrogen-donor ligands used are 2,6-bis[(dimethylamino)methyl]pyridine (NNN), N,N,N'-trimethyl-N'-(2-picolyl)ethylenediamine (pico), and N,N,N',N'',N''-pentamethyldiethylenetriamine (pmdeta). The chloro derivatives (3-5a) were obtained as yellow ionic complexes in excellent yields (81-93%). Crystals of 4a were obtained from methanol/diethyl ether and are monoclinic, space group P2(1)/c (No. 14), a = 15.0760(7) angstrom, b = 7.4468(8) angstrom, c = 13.553(2) angstrom, beta = 115.653(6)-degrees, and Z = 4. Refinement converged at R = 0.0325 (wR2 = 0.0663). The molecular structure shows a four-coordinate palladium center surrounded by the terdentate bound pico ligand and a chloride anion. There is no interaction of the palladium center with the second chloride anion (Pd-Cl2 greater-than-or-equal-to 4.2617 angstrom). The Pd-NMe bond distance (2.023(3) angstrom) is relatively short and is accompanied by a small trans N-Pd-N bond angle (168.03(12)-degrees). The methyl derivatives (3-5b) were also obtained in good yield (79-91%) via reaction of PdIMe(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine) with silver trifluoromethanesulfonate and the ligand. An alternative route, starting from PdMe2(tmeda), is reported for the synthesis of [PdMe(NNN)OTf (3b). Crystals of 3b were obtained from methanol/diethyl ether and are monoclinic, space group P2(1)/a (No. 14), a = 7.738(l) angstrom, b = 21.280(2) angstrom, c = 11.399(1) angstrom, beta = 92.05(1)-degrees, and Z = 4. Refinement converged at R = 0.066 (R(w) = 0.065). The molecular structure of Sb shows a terdentate coordination of the NNN ligand to the metal, with a relatively short Pd-N' bond distance (1.996(8) angstrom) and small N-Pd-N bond angle (161.7(3)-degrees). Yellow crystals of [PdMe(ONN')(tmeda)]OTf (8), with ONN' = 2-(hydroxymethyl)-6-[(dimethylamino)methyl]pyridine (7), were accidentally obtained from the reaction of [PdMe(MeCN)(tmeda)]OTf (I) with an impure sample of the NN'N ligand, containing the ONN' ligand. The molecular structure of 8 shows the ONN' ligand monodentate coordinated to the metal via its pyridyl nitrogen donor whereas the NMe2 and OH functionalities are free. The triflate anion is hydrogen bonded to the hydroxymethyl group with OH=O-(SO2CF3) = 2.759(3) angstrom and O-H-O = 173(4)-degrees. Crystals of [PdMe(ONN')(tmeda)]OTf (8) are triclinic, space group P1BAR (No. 2), a = 9.7902(14) angstrom, b = 10.0555(15) angstrom, c = 12.362(2) angstrom, alpha = 75.828(12)-degrees, beta = 81.234(12)-degrees, gamma = 84.836(11)-degrees, and Z = 2. Refinement converged at R = 0.032 (R(w) = 0.040). The first examples of simple arylpalladium(II) cations containing tridentate ligands were obtained m moderate to high yield (35-95%). The aryl groups studied differ in both steric and electronic properties. Conformational analysis by NMR of the NCCN moieties of the pico and pmdeta containing complexes showed the five-membered chelate rings in the complexes to occur selectively in one of the two possible conformations. The rotational-energy barriers of the aryl groups have been studied as a function of the ligand and were shown to increase in the order NNN < pico < pmdeta.This is explained in terms' of the positioning and orientation of the pyridyl and NMe2 groups around the metal center. The aryl rotation is found to be blocked in ortho-substituted aryl complexes, leading to atropisomerism in the pmdeta complex.

  DOI：

  10.1021/om00020a043