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Supramolecular Assemblies of Trinuclear Triangular Copper(II) Secondary Building Units through Hydrogen Bonds. Generation of Different Metal−Organic Frameworks, Valuable Catalysts for Peroxidative Oxidation of Alkanes

Supporting Info

Corrado Di Nicola, Yauhen Yu. Karabach,^† Alexander M. Kirillov,^† Magda Monari,*^‡ Luciano Pandolfo,*^§ Claudio Pettinari,* and Armando J. L. Pombeiro*^†

Department of Chemical Sciences, Via S. Agostino 1, University of Camerino, I-62032 Camerino (MC), Italy, Centro de Qumica Estrutural, Complexo I, Instituto Superior Tcnico, Av. Rovisco Pais, 1049-001 Lisbon, Portugal, Department of Chemistry G. Ciamician, University of Bologna, Via Selmi 2, I-40126 Bologna, Italy, and Department of Chemical Sciences, University of Padova, Via Marzolo 1, I-35131 Padova, Italy

Inorg. Chem., 2007, 46 (1), pp 221–230

DOI: 10.1021/ic061595n

Publication Date (Web): December 10, 2006

University of Camerino.

†

Instituto Superior Técnico.

To whom correspondence should be addressed. E-mail: magda.monari@unibo.it (M.M.), luciano.pandolfo@unipd.it (L.P.), claudio.pettinari@unicam.it (C.P.), pombeiro@ist.utl.pt. (A.J.L.P.). Phone: +39 051 2099559 (M.M.), +39 049 8275157 (L.P.), +39 0737 402234 (C.P.). +351 218419237 (A.J.L.P.). Fax: +39 051 2099456 (M.M.), +39 049 8275161 (L.P.), +39 0737 637345 (C.P.), +351 218464455 (A.J.L.P.).

‡

University of Bologna.

University of Padova.

Abstract

Formation of the trinuclear triangular copper derivative [Cu₃(μ₃-OH)(μ-pz)₃(EtCOO)₂(H₂O)]·H₂O, 1b (Hpz = pyrazole), has been simply achieved by addition of Hpz to a water solution of Cu(EtCOO)₂·H₂O and leaving the resulting solution to crystallize at ca. 12 °C. When the reaction and crystallization were carried out at a slightly higher temperature (18−22 °C), the compound [Cu₃(μ₃-OH)(μ-pz)₃(EtCOO)₂(H₂O)], 1c, formed. Single-crystal X-ray molecular structure determinations show that both compounds have analogous trinuclear triangular structures, but very different supramolecular assemblies, due mainly, but not only, to the crystallization molecule of H₂O in 1b. In particular, contrarily to the previously reported, strictly related, [Cu₃(μ₃-OH)(μ-pz)₃(EtCOO)₂(EtOH)], 1a, the propionate ions in 1b and 1c do not bridge different triangular units, whereas they are involved in intra- and intermolecular H-bonds, generating complex supramolecular 2-D MOFs. Compounds 1a and 1c act as remarkably active and selective catalysts or catalyst precursors for liquid biphasic (MeCN/H₂O) peroxidative oxidation of cyclohexane and cyclopentane to the corresponding alcohols and ketones.