{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,11]],"date-time":"2026-03-11T12:15:28Z","timestamp":1773231328612,"version":"3.50.1"},"reference-count":52,"publisher":"Wiley","issue":"22","license":[{"start":{"date-parts":[[2008,7,7]],"date-time":"2008-07-07T00:00:00Z","timestamp":1215388800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Inorg Chem"],"published-print":{"date-parts":[[2008,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The new water\u2010soluble 2D Cu\/Na coordination polymer [Cu(\u03bc\u2010dipic)<jats:sub>2<\/jats:sub>{Na<jats:sub>2<\/jats:sub>(\u03bc\u2010H<jats:sub>2<\/jats:sub>O)<jats:sub>4<\/jats:sub>}]<jats:italic><jats:sub>n<\/jats:sub><\/jats:italic><jats:bold>\u00b7<\/jats:bold>2<jats:italic>n<\/jats:italic>H<jats:sub>2<\/jats:sub>O (<jats:bold>1<\/jats:bold>) has been synthesized by self\u2010assembly in aqueous medium from copper(II) nitrate, dipicolinic acid (H<jats:sub>2<\/jats:sub>dipic) and sodium hydroxide in the presence of triethanolamine. It has been characterized by IR spectroscopy, FAB<jats:sup>+<\/jats:sup>\u2010MS, elemental and single\u2010crystal X\u2010ray diffraction analyses, the latter featuring a layered 2D metal\u2013organic structure that is extended to a 3D supramolecular assembly by extensive hydrogen bonding between adjacent layers and involving crystallization water molecules. Compound <jats:bold>1<\/jats:bold> has been shown to act as a catalyst precursor for the peroxidative oxidation of cyclohexane and cyclopentane to the corresponding cyclic ketones and alcohols by aqueous H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> in MeCN solution and in the absence of acid additives.(\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2008)<\/jats:p>","DOI":"10.1002\/ejic.200800355","type":"journal-article","created":{"date-parts":[[2008,7,7]],"date-time":"2008-07-07T02:16:22Z","timestamp":1215396982000},"page":"3423-3427","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":98,"title":["Self\u2010Assembled Two\u2010Dimensional Water\u2010Soluble Dipicolinate Cu\/Na Coordination Polymer: Structural Features and Catalytic Activity for the Mild Peroxidative Oxidation of Cycloalkanes in Acid\u2010Free Medium"],"prefix":"10.1002","volume":"2008","author":[{"given":"Marina V.","family":"Kirillova","sequence":"first","affiliation":[]},{"given":"Alexander M.","family":"Kirillov","sequence":"additional","affiliation":[]},{"given":"M. F\u00e1tima C.","family":"Guedes da Silva","sequence":"additional","affiliation":[]},{"given":"Armando J. L.","family":"Pombeiro","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2008,7,17]]},"reference":[{"key":"e_1_2_5_1_2","first-page":"415","volume":"3","author":"Nathan L. C.","year":"1993","journal-title":"Trends Inorg. Chem."},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108768102003890"},{"key":"e_1_2_5_3_2","unstructured":"\u00a0"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2007.10.030"},{"key":"e_1_2_5_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2006.12.016"},{"key":"e_1_2_5_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic7007446"},{"key":"e_1_2_5_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic049498m"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic034982v"},{"key":"e_1_2_5_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic034976z"},{"key":"e_1_2_5_10_2","unstructured":"\u00a0"},{"key":"e_1_2_5_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/cg060641r"},{"key":"e_1_2_5_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.inoche.2007.02.022"},{"key":"e_1_2_5_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2006.12.041"},{"key":"e_1_2_5_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2006.07.087"},{"key":"e_1_2_5_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2004.11.041"},{"key":"e_1_2_5_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/B407571D"},{"key":"e_1_2_5_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmcl.2004.06.018"},{"key":"e_1_2_5_18_2","doi-asserted-by":"publisher","DOI":"10.1023\/A:1011381504797"},{"key":"e_1_2_5_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/b503771a"},{"key":"e_1_2_5_20_2","unstructured":"\u00a0"},{"key":"e_1_2_5_21_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2007.11.007"},{"key":"e_1_2_5_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic701669x"},{"key":"e_1_2_5_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200601152"},{"key":"e_1_2_5_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic061595n"},{"key":"e_1_2_5_25_2","doi-asserted-by":"publisher","DOI":"10.1039\/b608790f"},{"key":"e_1_2_5_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/cg060310e"},{"key":"e_1_2_5_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200505216"},{"key":"e_1_2_5_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200500585"},{"key":"e_1_2_5_29_2","unstructured":"\u00a0"},{"key":"e_1_2_5_30_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature03311"},{"key":"e_1_2_5_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200604647"},{"key":"e_1_2_5_32_2","unstructured":"Synthesis of [Cu(\u03bc\u2010dipic)2{Na2(\u03bc\u2010H2O)4}]n\u00b72nH2O (1): To an aqueous solution (10.0 mL) containing Cu(NO3)2\u00b72.5H2O (1.00 mmol 233 mg) and HNO3(1.00 mmol) [the acid was added to avoid spontaneous hydrolysis of the metal salt] were added dropwise triethanolamine (1.00 mmol 130 \u03bcL) and an aqueous solution (4.0 mL) of NaOH (160 mg 4.00 mmol) and solid H2dipic (84 mg 0.50 mmol) in this order and with continuous stirring in air at ambient temperature. The resulting clear blue solution was stirred overnight then passed through a filter concentrated under reduced pressure to one half of its volume and kept in a beaker in air at ambient temperature. Light blue X\u2010ray quality crystals were formed in 2\u20133 weeks from a deep blue oily solution then collected gently wiped with a filter paper and dried in air to furnish compound1in ca. 70\u2009% yield based on H2dipic. Compound1is soluble in H2O (S25 \u00b0C\u2248 15 mg\u2009mL\u20131) and can be recrystallized from an aqueous solution in the original form. C14H18CuN2Na2O14(547.8): calcd. C 30.69 H 3.31 N 5.11; found C 30.28 H3.04 N 5.09. FAB+\u2010MS (m\u2010nitrobenzylalcohol):m\/z= 462[Cu(dipic)2+ 3Na]+ 440 [Cu(dipic)2Na2+ H]+ 396 [Cu(dipic)2+ 3H]+. IR (KBr selected bands):$\\tilde {\\nu}$= 3407 (vs. br) and 3108 (w sh) \u03bd(H2O) 1685 (sh) 1621 (vs. br) and 1591 (sh) \u03bdas(COO) + \u03b4(H2O) 1421 (s) and 1383 (vs. br) \u03bds(COO) 1279 (s) 1186 (m) 1156 (w) 1081 (s) 1043 (w) 997 (w) 913 (s) 855 (w) 822 (m) 768 (s) 733 (s) 689 (m) 510 (m) 444 (w) and 420 (w) (other bands) cm\u20131. All characterization procedures were performed with the instruments and according to the techniques previously described.[9]"},{"key":"e_1_2_5_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200505092"},{"key":"e_1_2_5_34_2","unstructured":"X\u2010ray crystal structure determination: X\u2010ray data were collected with an Enraf\u2013Nonius CAD4 diffractometer equipped with graphite monochromator and by using Mo\u2010K\u03b1radiation (\u03bb= 0.71073 \u00c5). The structure was solved by direct methods with the SHELXS\u201097 program.[11]A semiempirical absorption correction was applied.[12]The structure was refined with the SHELXL\u201097 program.[11]All hydrogen atoms were located. Crystal data for1: C14H18CuN2Na2O14 M= 547.82 monoclinic space groupP2\/c a= 9.7626(12) \u00c5 b= 7.9756(10) \u00c5 c= 12.9066(13) \u00c5 V= 1004.9(2) \u00c53 Z= 2 Dc= 1.811 g\u2009cm\u20133 F000= 558 \u03bc= 1.210 mm\u20131 T= 293 K 2026 reflections collected 1624 reflections withI\u2009>\u20092\u03c3(I) (Rint= 0.0217) GoF = 1.100 R1= 0.0281 wR2= 0.0736. CCDC\u2010CCDC\u2010683529 contains the supplementary crystallographic data for1. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_5_35_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"},{"key":"e_1_2_5_36_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0567739468000707"},{"key":"e_1_2_5_37_2","doi-asserted-by":"publisher","DOI":"10.1080\/00958970412331281773"},{"key":"e_1_2_5_38_2","unstructured":"It is interesting to note that according to a search in the CSD [2]the encountered [M2(\u03bc\u2010Ocarboxylate)(\u03bc\u2010H2O)2] core with bridging carboxylate oxygen and two \u03bc\u2010H2O molecules completing the coordination sphere of two metal (M) atoms appears to be rarely observed [only 7 matches; CSD refcodes: ALOWUT (Ca) NOVJUD (Na) NOLGOK and RUHHUX (Ba) KAMYON VENDUN01 and YEHBUJ (K)] in contrast to numerous structures (ca. 107 hits) bearing simpler [M2(\u03bc\u2010Ocarboxylate)(\u03bc\u2010H2O)] fragments."},{"key":"e_1_2_5_39_2","unstructured":"\u00a0"},{"key":"e_1_2_5_40_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.76.301"},{"key":"e_1_2_5_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja963899m"},{"key":"e_1_2_5_42_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2006.04.026"},{"key":"e_1_2_5_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2006.05.030"},{"key":"e_1_2_5_44_2","doi-asserted-by":"publisher","DOI":"10.1080\/00958970600717884"},{"key":"e_1_2_5_45_2","unstructured":"Peroxidative oxidation of cyclohexane and cyclopentane: The catalyst precursor1(5.0 mg 9.2 \u03bcmol) used as a solid was mixed with the cycloalkane (1.25 mmol) CH3NO2(internal standard for GC analysis 0.50 mL of its 1.4Msolution in MeCN) acetonitrile (4.20 mL) and H2O2(2.50 mmol 50\u2009% in H2O 0.17 mL) in this order. The resulting reaction mixtures were vigorously stirred in thermostatted (50 \u00b0C) Pyrex cylindrical vessels for 5 h at atmospheric air pressure. The product analysis was performed as follows: a sample was taken from the reaction mixture treated with an excess of solid PPh3(for prior reduction[17]of cycloalkyl hydroperoxides that are the main primary products) and then analyzed by GC by using a Fisons Instruments GC 8000 series gas chromatograph with a DB\u2010624 (J&W) capillary column and the Jasco\u2010Borwin v.1.50 software revealing the formation of the following mixtures: cyclohexanol (9.3\u2009%) + cyclohexanone (1.8\u2009%) and cyclopentanol (9.1\u2009%) + cyclopentanone (0.8\u2009%) for cyclohexane and cyclopentane oxidations respectively. Blank experiments were performed for both cycloalkanes under similar reaction conditions which confirmed that no oxidation products were obtained in the absence of precursor1. Additional catalytic experiments were performed in the presence of (i) either 5 or 10 equiv. (relative to1) of concentrated HNO3(46\u201392 \u03bcmol 63\u2009% in H2O) or (ii) radical traps CBrCl3 2 6\u2010di\u2010tert\u2010butyl\u20104\u2010methylphenol (BHT) or Ph2NH (2.50 mmol of each in a separate batch) displaying an almost complete suppression of catalytic activity of1(only traces of products below 0.3\u2009% were observed)."},{"key":"e_1_2_5_46_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1381-1169(02)00196-6"},{"key":"e_1_2_5_47_2","unstructured":"This activity has been achieved by using slightly different (relative to those described[16]) reaction parameters i.e. catalyst precursor1(3.0 mg 5.5 \u03bcmol) cyclohexane (10.0 mmol) acetonitrile (3.80 mL) and H2O2(10.0 mmol 50\u2009% in H2O 0.68 mL)."},{"key":"e_1_2_5_48_2","unstructured":"EPR spectra of1were recorded (following a reviewer's suggestion) on solid crystalline samples or frozen aqueous solutions by using a Bruker ESP300E X\u2010band spectrometer equipped with an ER 4111 VT variable\u2010temperature unit. Typical patterns for CuII(I= 3\/2) withg= 2.22 andA= 130 G (with poorly resolved hyperfine coupling) were observed for both solid (298 K) and solution (100 K) samples of1. A broad signal (g= 2.16) without hyperfine coupling was obtained for a solid sample at 100 K."},{"key":"e_1_2_5_49_2","unstructured":"\u00a0"},{"key":"e_1_2_5_50_2","doi-asserted-by":"publisher","DOI":"10.1039\/b306382h"},{"key":"e_1_2_5_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200303147"},{"key":"e_1_2_5_52_2","unstructured":"Additional blank experiments carried out under similar reaction conditions [16]but in the absence of compound1and in the presence of a catalytic amount (10 \u03bcmol) of Na2CO3or K2CO3 reveal no activity in the oxidation of cyclohexane (i.e. only traces of products below 0.2\u2009% of the total yield have been detected). Moreover the activity of1is not promoted to any extent by the addition of potassium or sodium carbonate."}],"container-title":["European Journal of Inorganic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fejic.200800355","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejic.200800355","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/ejic.200800355","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejic.200800355","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T20:10:51Z","timestamp":1760386251000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/ejic.200800355"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2008,7,17]]},"references-count":52,"journal-issue":{"issue":"22","published-print":{"date-parts":[[2008,8]]}},"alternative-id":["10.1002\/ejic.200800355"],"URL":"https:\/\/doi.org\/10.1002\/ejic.200800355","archive":["Portico"],"relation":{},"ISSN":["1434-1948","1099-0682"],"issn-type":[{"value":"1434-1948","type":"print"},{"value":"1099-0682","type":"electronic"}],"subject":[],"published":{"date-parts":[[2008,7,17]]},"assertion":[{"value":"2008-04-07","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2008-07-17","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}