Synthesis, structure, and kinetic studies on [RuCl2(NCCH3)2(cod)]

摘要: [RuCl2(NCCH3)2(cod)], an alternative starting material to [RuCl2(cod)] n for the preparation of ruthenium(II) complexes, has been prepared from polymer compound and isolated in yields up 87% using a new work-up procedure. The obtained as yellow solid without water crystallization. complexes [RuCl2(NCR)2(cod)] spontaneously transform into dimers [Ru2Cl(μ-Cl)3(cod)2(NCR)] (R = Me, Ph). 1H NMR kinetic experiments these transformations evidenced first-order behavior. [RuCl2(NCPh)2(cod)] dimerizes slower by factor ten than [RuCl2(NCCH3)2(cod)]. following activation parameters, ΔH # = 114 ± 3 kJ mol−1 ΔS # = 66 ± 9 J K−1 mol−1 R = CH3CN (ΔG # = 94 ± 5 kJ mol−1, 298.15 K) # = 122 ± 2 kJ mol−1 # = 75 ± 6 J K−1 mol−1 R = Ph # = 100 ± 4 kJ mol−1, 298.15 K), have calculated rate constants temperature range 294–323 K. parameters are agreement with two-step mechanism dissociation aceto...