RT Journal Article
T1 Three-Component Copper-Phosphonate-Auxiliary Ligand Systems: Proton Conductors and Efficient Catalysts in Mild Oxidative Functionalization of Cycloalkanes
A1 Armakola, Eirini
A1 Pérez-Colodrero, Rosario Mercedes
A1 Bazaga-García, Montse
A1 Salcedo, Inés R.
A1 Choquesillo-Lazarte, Duane
A1 Cabeza-Díaz, Aurelio
A1 Kirillova, Marina V.
A1 Kirillov, Alexander M.
A1 Demadis, Konstantinos D.
K1 Conductividad eléctrica
K1 Hidrocarburos
AB The synthesis, structural characterization, topological analysis, proton conductivity, and catalytic properties are reported of two Cu(II)-based compounds, namely a dinuclear Cu(II) complex [Cu2(μ-VPA)2(phen)2(H2O)2]· 8H2O (1) (H2VPA = vinylphosphonic acid, phen = 1,10- phenanthroline) and a 1D coordination polymer [Cu(μ- SO4)(phen)(H2O)2]∞ (2). Their structural features and Hbonding interactions were investigated in detail, showing that the metal−organic structures of 1 and 2 are extended by multiple hydrogen bonds to more complex 2D or 1D Hbonded architectures with the kgd [Shubnikov plane net(3.6.3.6)/dual] and SP 1-periodic net (4,4)(0,2) topology, respectively. These nets are primarily driven by the H-bonding interactions involving water ligands and H2O molecules of crystallization; besides, the (H2O)4/(H2O)5 clusters were identified in 1. Both 1 and 2 are moderate proton conductors, with proton conductivity values, σ = 3.65 × 10−6 and 3.94 × 10−6 S·cm−1, respectively (measured at 80 °C and 95% relative humidity). Compounds 1 and 2 are also efficient homogeneous catalysts for the mild oxidative functionalization of C5−C8 cycloalkanes (cyclopentane, cyclohexane, cycloheptane, and cyclooctane), namely for the oxidation by H2O2 to give cyclic alcohols and ketones and the hydrocarboxylation by CO/H2O and S2O82− to the corresponding cycloalkanecarboxylic acids as major products. The catalytic reactions proceed under mild conditions (50−60 °C) in aqueous acetonitrile medium, resulting in up to 34% product yields based on cycloalkane substrate.
PB ACS publications
YR 2018
FD 2018-08-13
LK https://hdl.handle.net/10630/20988
UL https://hdl.handle.net/10630/20988
LA eng
NO Inorg. Chem. 2018, 57, 10656−10666
NO Proyecto MAT2016-77648-R del MINECO y proyecto FQM-1656 de la  Junta de Andalucía
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 19 ene 2026