Bringing an "old" biological buffer to coordination chemistry: new 1D and 3D coordination polymers with [Cu(4)(Hbes)(4)] cores for mild hydrocarboxylation of alkanes.

New water-soluble 1D and 3D Cu(II)/Na coordination polymers 1-3 bearing unprecedented [Cu(4)(Hbes)(4)] cores have been easily generated by aqueous-medium self-assembly and fully characterized, thus opening up the use of the common biological buffer H(3)bes, (HO(3)SCH(2)CH(2))N(CH(2)CH(2)OH)(2), in synthetic coordination chemistry. Apart from representing the first isolated and structurally characterized coordination compounds derived from H(3)bes, 1-3 show a remarkable promoting effect in the mild aqueous-medium hydrocarboxylation, by CO and H(2)O, of gaseous alkanes (C(3)H(8) and n-C(4)H(10)) to the corresponding carboxylic acids, which are obtained in up to 95% yields based on the alkane.

Mono-, di- and polynuclear copper(II) compounds derived from N-butyldiethanolamine: structural features, magnetism and catalytic activity for the mild peroxidative oxidation of cyclohexane.

The new mononuclear [Cu(Hbdea)(2)].2Hdnba (), dinuclear [Cu(2)(mu-Hbdea)(2)(N(3))(2)] () and [Cu(2)(mu-Hbdea)(2)(pta)(2)].2H(2)O (), and 1D polymeric [Cu(2)(mu-Hbdea)(2)(mu-tpa)](n).2nH(2)O () copper(II) compounds have been prepared by self-assembly, in aqueous alkali medium and at ambient conditions, from Cu(II) acetate, N-butyldiethanolamine (H(2)bdea) and the corresponding auxiliary reagents, 3,5-dinitrobenzoic acid (Hdnba), sodium azide, p-toluic acid (Hpta) and terephthalic acid (H(2)tpa), respectively. They have been fully characterized by IR spectroscopy, FAB-MS(+), elemental and single-crystal X-ray diffraction analyses, the latter also revealing intensive intermolecular hydrogen bonding in , resulting in the extension of the structural motifs and generation of tetrameric aggregates (in ) and 1D (in ) or 2D (in ) supramolecular networks. All compounds constitute the first examples of Cu complexes derived from N-butyldiethanolamine, while represents also the first coordination polymer bearing this ligand. Magnetic susceptibility measurements reveal that compound follows the Curie-Weiss law, whereas follow the Bleaney-Bowers dinuclear model displaying antiferromagnetic coupling. Compounds act as valuable catalyst precursors for the mild peroxidative oxidation of cyclohexane, by aqueous H(2)O(2) in acidic MeCN medium, to cyclohexanol and cyclohexanone with overall yields up to 38%. The effects of various acid additives (promoters) have been studied, showing the preferable use of trifluoroacetic (TFA), nitric and hydrochloric acids.