(3-tolyl)[2,6-bis((dimethylamino)methyl)pyridine]palladium trifluoromethanesulfonate | 157045-34-6

• 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: (3-tolyl)[2,6-bis((dimethylamino)methyl)pyridine]palladium trifluoromethanesulfonate
• CAS: 157045-34-6
• 化学式: CF₃O₃S*C₁₈H₂₆N₃Pd
• 分子量: 539.915
• InChiKey: WRRNMDRDPNEWRK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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反应信息

• 作为产物：
  描述：

  (3-tolyl)(N,N,N',N'-tetramethylethylenediamine)Pd(acetonitrile) trifluoromethanesulfonate 、 2,6-bis<(dimethylamino)methyl>pyridine 以 丙酮 为溶剂， 以75%的产率得到(3-tolyl)[2,6-bis((dimethylamino)methyl)pyridine]palladium trifluoromethanesulfonate
  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