The monometallic complex [Pd(L)(PPh 3 )] (mono-Pd) was synthesized using a potentially tridentate hydrazone (H 2 L) and used as precursor to prepare a heterobimetallic ruthenium (II)-palladium (II) complex [Cl 2 (p-cymene)Ru(μ-L)Pd (PPh 3 )] (Ru-Pd). Mono-Pd and Ru-Pd were characterized by fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-Vis), 1 H, 13 C{ 1 H} and 31 P{ 1 H} nuclear magnetic ressonance(NMR) spectroscopy, elemental analysis, cyclic voltammetry, matrix-assisted laser desorption/ ionization -time of flight (MALDI-TOF) mass spectrometry, and computational methods. The mono-Pd was additionally studied by single-crystal X-ray diffraction. The complex [RuCl 2 (p-cymene)(Isoniazid)] (mono-Ru) was also obtained following literature methods aiming a comparison in the catalytic activity. The ring opening metathesis polymerization (ROMP) of norbornene (NBE) using mono-Ru or Ru-Pd as precatalysts in the presence of ethyl diazoacetate (EDA) was evaluated as a function of time (10-60 min) using [NBE]/[EDA]/[Ru] = 5000/28/1 at 50 C. The time increases produced good yields of polyNBE, reaching 38% and 46% for mono-Ru and Ru-Pd, respectively. The polyNBE produced was measured by size-exclusion chromatography (SEC) and reached an order of magnitude of 10 5 gÁmol À1 of M n , with Ð values ranging from 2.51 to 1.86 for mono-Ru and from 3.50 to 1.66 for Ru-Pd. The catalytic activity of mono-Pd and Ru-Pd on ethylene polymerization was assessed with a range of [Al]/[Pd] molar ratio between 350 and 1750, 30-70 C temperature, 2 to 4 h reaction time, and total reaction volume of 25 and 50 ml. Mono-Pd achieved an activity of 22.80 kg PE (mol Pd) À1 h À1 at 60 C after 4 h using [Al]/[Pd] = 1050, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. For Ru-Pd, an activity of 20.35 kg PE (mol Pd) À1 h À1 at 60 C after 4 h was obtained using [Al]/[Pd] = 1750, 7 μmol
Monometallic [RuCl2(η6-p-cymene)(pipNH2)] (mono-Ru) and heterobimetallic [RuCl2(p-cymene)](μ-Schiff-pip)Ni(PPh3)Cl] (Ru-Ni) complexes were successfully synthesized. They were fully characterized by FTIR, UV-Vis, and NMR spectroscopic studies, elemental analysis, cyclic voltammetry and computational studies. Complex...
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