Mild homogeneous oxidation and hydrocarboxylation of cycloalkanes catalyzed by novel dicopper(II) aminoalcohol-driven cores

作者: Tiago A. Fernandes , Vânia André , Alexander M. Kirillov , Marina V. Kirillova

DOI: 10.1016/J.MOLCATA.2016.07.050

关键词:

摘要: Abstract N-benzylethanolamine (Hbea) and triisopropanolamine (H3tipa) were applied as unexplored aminoalcohol N,O-building blocks for the self-assembly generation of two novel dicopper(II) compounds, [Cu2(μ-bea)2(Hbea)2](NO3)2 (1) [Cu2(H3tipa)2(μ-pma)]·7H2O (2) {H4pma = pyromellitic acid}. These isolated stable aqua-soluble microcrystalline products fully characterized by IR spectroscopy, ESI–MS(±), single-crystal X-ray diffraction, latter revealing distinct Cu2 cores containing five-coordinate copper(II) centers with {CuN2O3} or {CuNO4} environments. Compounds 1 2 used homogeneous catalysts mild oxidation C5–C8 cycloalkanes to give corresponding cyclic alcohols ketones in up 23% overall yields based on cycloalkane. The reactions proceed aqueous acetonitrile medium at 50 °C using H2O2 an oxidant. effects different reaction conditions studied, including type loading catalyst, amount kind acid promoter, water concentration. Despite fact that acids (HNO3, H2SO4, HCl, CF3COOH) promote alkanes, is exceptionally fast presence a catalytic resulting TOF values 430 h−1. Although typically strongly inhibits alkane oxidations due reduction concentration lowering solubility, systems comprising we observed significant growth (up 5-fold) initial rate cyclohexane increasing H2O mixture. bond-, regio- stereo-selectivity parameters investigated linear, branched, substrates. Both compounds also catalyze hydrocarboxylation cycloalkanes, CO, K2S2O8, water/acetonitrile 60 °C, cycloalkanecarboxylic 38% cycloalkanes.

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