{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,5]],"date-time":"2026-03-05T19:39:40Z","timestamp":1772739580715,"version":"3.50.1"},"reference-count":100,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2014,1,30]],"date-time":"2014-01-30T00:00:00Z","timestamp":1391040000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2014,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>[CoCl(\u03bc\u2010Cl)(Hpz<jats:sup>Ph<\/jats:sup>)<jats:sub>3<\/jats:sub>]<jats:sub>2<\/jats:sub> (<jats:bold>1<\/jats:bold>) and [CoCl<jats:sub>2<\/jats:sub>(Hpz<jats:sup>Ph<\/jats:sup>)<jats:sub>4<\/jats:sub>] (<jats:bold>2<\/jats:bold>) were obtained by reaction of CoCl<jats:sub>2<\/jats:sub> with HC(pz<jats:sup>Ph<\/jats:sup>)<jats:sub>3<\/jats:sub> and Hpz<jats:sup>Ph<\/jats:sup>, respectively (Hpz<jats:sup>Ph<\/jats:sup>=3\u2010phenylpyrazole). The compounds were isolated as air\u2010stable solids and fully characterized by IR and far\u2010IR spectroscopy, MS(ESI+\/\u2212), elemental analysis, cyclic voltammetry (CV), controlled potential electrolysis, and single\u2010crystal X\u2010ray diffraction. Electrochemical studies showed that <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> undergo single\u2010electron irreversible Co<jats:sup>II<\/jats:sup>\u2192Co<jats:sup>III<\/jats:sup> oxidations and Co<jats:sup>II<\/jats:sup>\u2192Co<jats:sup>I<\/jats:sup> reductions at potentials measured by CV, which also allowed, in the case of dinuclear complex <jats:bold>1<\/jats:bold>, the detection of electronic communication between the Co centers through the chloride bridging ligands. The electrochemical behavior of models of <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> were also investigated by density functional theory (DFT) methods, which indicated that the vertical oxidation of <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> (that before structural relaxation) affects mostly the chloride and pyrazolyl ligands, whereas adiabatic oxidation (that after the geometry relaxation) and reduction are mostly metal centered. Compounds <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> and, for comparative purposes, other related scorpionate and pyrazole cobalt complexes, exhibit catalytic activity for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone under mild conditions (room temperature, aqueous H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub>). In\u2005situ X\u2010ray absorption spectroscopy studies indicated that the species derived from complexes <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> during the oxidation of cyclohexane (i.e., Ox\u2010<jats:bold>1<\/jats:bold> and Ox\u2010<jats:bold>2<\/jats:bold>, respectively) are analogous and contain a Co<jats:sup>III<\/jats:sup> site. Complex <jats:bold>2<\/jats:bold> showed low in\u2005vitro cytotoxicity toward the HCT116 colorectal carcinoma and MCF7 breast adenocarcinoma cell lines.<\/jats:p>","DOI":"10.1002\/asia.201301331","type":"journal-article","created":{"date-parts":[[2014,1,30]],"date-time":"2014-01-30T08:33:15Z","timestamp":1391070795000},"page":"1132-1143","source":"Crossref","is-referenced-by-count":41,"title":["Cobalt Complexes with Pyrazole Ligands as Catalyst Precursors for the Peroxidative Oxidation of Cyclohexane: X\u2010ray Absorption Spectroscopy Studies and Biological Applications"],"prefix":"10.1002","volume":"9","author":[{"given":"Telma","family":"F.\u2005S. Silva","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lu\u00edsa","family":"M.\u2005D.\u2005R.\u2005S. Martins","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"M. F\u00e1tima C.","family":"Guedes\u2005da\u2005Silva","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Maxim L.","family":"Kuznetsov","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Alexandra R.","family":"Fernandes","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ana","family":"Silva","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chun\u2010Jern","family":"Pan","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jyh\u2010Fu","family":"Lee","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Bing\u2010Joe","family":"Hwang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Armando","family":"J.\u2005L. Pombeiro","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2014,1,30]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"crossref","DOI":"10.1142\/p148","volume-title":"Scorpionates, The Coordination Chemistry of Polypyrazolylborate Ligands","author":"Trofimenko S.","year":"1999"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1142\/p527"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2003-37339"},{"key":"e_1_2_6_5_2","volume-title":"Comprehensive Coordination Chemistry II, Vol.\u20056","author":"Bernhardt R. V.","year":"2004"},{"key":"e_1_2_6_6_2","volume-title":"Encyclopedia of Inorganic Chemistry, Vol.\u2005II, 2nd\u2005ed.","author":"Kr\u00e4utler B.","year":"2005"},{"key":"e_1_2_6_7_2","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"crossref","unstructured":"C.Pettinari C.Santini \u201cPolypyrazolylborate and Scorpionate Ligands\u201d inComprehensive Coordination Chemistry II: From Biology to Nanotechnology Vol.\u20051(Eds.: J.\u2005A. McCleverty T.\u2005J. Meyer) Elsevier Pergamon (APS) Amsterdam 2003 pp.\u2005159\u2013210;","DOI":"10.1016\/B0-08-043748-6\/01179-8"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(04)00131-6"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/b413121e"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2013.01.027"},{"key":"e_1_2_6_12_2","unstructured":"\u00a0"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200713v"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic201714c"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2010.12.036"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic100966u"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201000018"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200900660"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/b911990f"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1351\/PAC-CON-08-10-08"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic801254b"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcata.2008.01.022"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200700529"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcata.2006.09.038"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1107\/S1600536807024671"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/b611209a"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2004.11.005"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcata.2012.10.024"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic400024r"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcata.2013.05.022"},{"key":"e_1_2_6_31_2","unstructured":"L.\u2005M.\u2005D.\u2005R.\u2005S. Martins M.\u2005P. Almeida S.\u2005A.\u2005C. Carabineiro J.\u2005L. Figueiredo A.\u2005J.\u2005L. Pombeiro ChemCatChem\u00ad2013 DOI:;"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3cy00552f"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2dt11577h"},{"key":"e_1_2_6_34_2","unstructured":"\u00a0"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2004.03.020"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2007.07.024"},{"key":"e_1_2_6_37_2","volume-title":"Metallotherapeutic Drugs and Metal\u2010Based Diagnostic Agents: The Use of Metals in Medicine","author":"Chao H.","year":"2005"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1089\/ars.2010.3663"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.2174\/138161210791209009"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1007\/s00204-008-0313-y"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/tx049842s"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1007\/s10534-011-9496-4"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(89)87104-9"},{"key":"e_1_2_6_44_2","unstructured":"\u00a0"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00331a030"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1016\/B0-08-043748-6\/01185-3"},{"key":"e_1_2_6_47_2","first-page":"77","volume-title":"Encyclopaedia of Electrochemistry, Vol.\u20057\u2009A","author":"Pombeiro A. J. L.","year":"2006"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200601095"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2005.07.111"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0503737"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic025835k"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1039\/b815001j"},{"key":"e_1_2_6_53_2","unstructured":"\u00a0"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic061595n"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1039\/b608790f"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200505216"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200500585"},{"key":"e_1_2_6_57_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200500585"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200400991"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1381-1169(03)00420-5"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1039\/b005513l"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja072531u"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200700980"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcata.2008.10.027"},{"key":"e_1_2_6_64_2","unstructured":"\u00a0"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1631-0748(03)00021-3"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1381-1169(02)00196-6"},{"key":"e_1_2_6_67_2","doi-asserted-by":"publisher","DOI":"10.1039\/b101442k"},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(99)00233-1"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2009.08.006"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200800355"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2007.02.025"},{"key":"e_1_2_6_72_2","unstructured":"\u00a0"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic801753t"},{"key":"e_1_2_6_74_2","doi-asserted-by":"publisher","DOI":"10.1021\/cs200237m"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2009.08.016"},{"key":"e_1_2_6_76_2","first-page":"362","volume-title":"X\u2010Ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES","year":"1988"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0205968"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmcl.2005.12.019"},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1092472"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2006.12.005"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.addr.2012.01.007"},{"key":"e_1_2_6_82_2","unstructured":"\u00a0"},{"key":"e_1_2_6_83_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(01)00299-5"},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(91)86433-Q"},{"key":"e_1_2_6_85_2","unstructured":"Bruker APEX2& SAINT; AXS Inc. Madison WI 2004;"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"},{"key":"e_1_2_6_87_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889899006020"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_6_89_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_6_90_2","unstructured":"Gaussian\u200509 revision\u2005A.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone B. Mennucci G.\u2005A. Petersson H. Nakatsuji M. Caricato X. Li H.\u2005P. Hratchian A.\u2005F. Izmaylov J. Bloino G. Zheng J.\u2005L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J.\u2005A. Montgomery \u2005Jr. J.\u2005E. Peralta F. Ogliaro M. Bearpark J.\u2005J. Heyd E. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov R. Kobayashi J. Normand K. Raghavachari A. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega J.\u2005M. Millam M. Klene J.\u2005E. Knox J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels O. Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski D.\u2005J. Fox Gaussian Inc. Wallingford CT 2009."},{"key":"e_1_2_6_91_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0898-8838(08)60070-7"},{"key":"e_1_2_6_92_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1096-987X(199910)20:13<1391::AID-JCC6>3.0.CO;2-J"},{"key":"e_1_2_6_93_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.10257"},{"key":"e_1_2_6_94_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00521a020"},{"key":"e_1_2_6_95_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.440939"},{"key":"e_1_2_6_96_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(86)80192-6"},{"key":"e_1_2_6_97_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(00)00166-4"},{"key":"e_1_2_6_98_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.452288"},{"key":"e_1_2_6_99_2","doi-asserted-by":"publisher","DOI":"10.1515\/dmdi-2013-0015"}],"container-title":["Chemistry \u2013 An Asian Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fasia.201301331","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/asia.201301331","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,8]],"date-time":"2025-10-08T18:51:49Z","timestamp":1759949509000},"score":1,"resource":{"primary":{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/10.1002\/asia.201301331"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,1,30]]},"references-count":100,"journal-issue":{"issue":"4","published-print":{"date-parts":[[2014,4]]}},"alternative-id":["10.1002\/asia.201301331"],"URL":"https:\/\/doi.org\/10.1002\/asia.201301331","archive":["Portico"],"relation":{},"ISSN":["1861-4728","1861-471X"],"issn-type":[{"value":"1861-4728","type":"print"},{"value":"1861-471X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2014,1,30]]}}}