contrasted with previous proton transfer studies of other metal clusters which exhibit anomalously large kinetic deuterium isotope effects, and it is tentatively concluded that these effects are associated with strictly intramolecular hydrogen transfer as opposed to the anion-assisted intermolecular process reported here. The carbonyl group ligand dynamics for 1−3 are reported.
在-80至+25的温度范围内,使用CF 3 CO 2 X和CF 3 SO 3 X(X = H或D)重新检查了Ru 3(CO)10(μ-NO)-(1)的质子化。使用13 C NMR技术的℃。对于这两种酸,质子化的动力学部位是亚硝基团的氧,得到的Ru 3(CO)9(μ 3 -CO)(μ 3 -NOH)(2)。质子转移到
金属核的速率,得到Ru 3(CO)10(μ-NO)(μ-H)(3),对于质子和
氘代病例来说大致相同。这些结果与先前对其他表现出异常大的动力学
氘同位素效应的
金属簇的质子转移研究进行了对比,并初步得出结论,这些作用与严格的分子内氢转移有关,与此处报道的阴离子辅助的分子间过程相反。为羰基
配体动力学1 - 3中报告。