{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,10]],"date-time":"2026-04-10T22:31:28Z","timestamp":1775860288209,"version":"3.50.1"},"reference-count":43,"publisher":"Walter de Gruyter GmbH","issue":"7","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2009,5,31]]},"abstract":"<jats:p>The V-scorpionate vanadium complexes [VCl<jats:sub>3<\/jats:sub>{HC(pz)<jats:sub>3<\/jats:sub>}] (pz = pyrazolyl) and [VCl<jats:sub>3<\/jats:sub>{SO<jats:sub>3<\/jats:sub>C(pz)<jats:sub>3<\/jats:sub>}] catalyze cyclohexane oxidation with dioxygen, to cyclohexanol (the main product) and cyclohexanone, under solvent-free conditions. [VCl<jats:sub>3<\/jats:sub>{HC(pz)<jats:sub>3<\/jats:sub>}] provides the best activity (13 % conversion into the ketone and alcohol, with high selectivity, at the O<jats:sub>2<\/jats:sub> pressure of 15 atm, at 140 \u00baC, 18 h reaction time). The reaction is further promoted (to 15 % conversion) by pyrazinecarboxylic acid (PCA). The use of C- or O-radical traps supports the involvement of a free-radical reaction mechanism. Several reaction parameters have been varied in a systematic study, directed toward optimization of the process.<\/jats:p>","DOI":"10.1351\/pac-con-08-10-08","type":"journal-article","created":{"date-parts":[[2009,6,1]],"date-time":"2009-06-01T20:02:14Z","timestamp":1243886534000},"page":"1217-1227","source":"Crossref","is-referenced-by-count":54,"title":["Scorpionate complexes of vanadium(III or IV) as catalyst precursors for solvent-free cyclohexane oxidation with dioxygen"],"prefix":"10.1515","volume":"81","author":[{"given":"Gopal S.","family":"Mishra","sequence":"first","affiliation":[{"name":"1Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal"}]},{"given":"Telma F. S.","family":"Silva","sequence":"additional","affiliation":[{"name":"2\u00c1rea Cient\u00edfica de F\u00edsica, ISEL, R. Conselheiro Em\u00eddio Navarro, 1959-007, Lisbon, Portugal"}]},{"given":"Lu\u00edsa M. D. R. S.","family":"Martins","sequence":"additional","affiliation":[{"name":"1Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal"}]},{"given":"Armando J. L.","family":"Pombeiro","sequence":"additional","affiliation":[{"name":"1Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal"}]}],"member":"374","reference":[{"key":"ref91","doi-asserted-by":"publisher","author":"Kirillova","DOI":"10.1016\/j.jcat.2007.02.025,(a)M..........J..da.J.L.Pombeiro.J.Catal.248,130(2007)"},{"key":"ref321","doi-asserted-by":"publisher","author":"Fink","DOI":"10.1039\/b101442k,(a)G.B.Shul'pin.N.Kozlov.V.Nizova.Suss-.Stanislas.Kitaygorodskiy.S.Kulikova.PerkinTrans.21351(2001)"},{"key":"ref361","doi-asserted-by":"publisher","author":"Nicola","DOI":"10.1021\/ic061595n,(c)C.Di.Y.Karabach.M.Kirillov.Monari.Pandolfo.Pettinari.J.L.Pombeiro.Inorg.Chem.46,221(2007)"},{"key":"ref211","doi-asserted-by":"publisher","author":"Bonnet","journal-title":"Green Chem","DOI":"10.1039\/b600903d....P.Simonto..8,556(2006)"},{"key":"ref241","doi-asserted-by":"publisher","DOI":"10.1023\/A:1026334921387..S.Mishra...Chem.28,913(2003)","article-title":"Transition","author":"Kumar","journal-title":"Met"},{"key":"ref281","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200390120,(a)M.Vennat.Herson.M.Bregeault.B.Shul'pin.Eur.J.Inorg.Chem.908(2003)"},{"key":"ref411","doi-asserted-by":"publisher","author":"Silva","DOI":"10.1002\/ejic.200400991,(h)A.M.Kirillov.Haukka....da.J..Pombeiro.Eur.J.Inorg.Chem.2071(2005)"},{"key":"ref221","doi-asserted-by":"publisher","journal-title":"Mol Catal Chem","DOI":"10.1016\/j.molcata.2005.05.035.S.Mishra.J.L.Pombeiro.J...A:.239,96(2005)"},{"key":"ref251","doi-asserted-by":"publisher","journal-title":"Mol Catal Chem","DOI":"10.1016\/j.molcata.2004.11.022.S.Mishra.J.Lakshmi.Kumar.J...A:.230,35(2005)"},{"key":"ref401","doi-asserted-by":"publisher","author":"Silva","DOI":"10.1002\/anie.200500585,(g)A.M.Kirillov.N.Kopylovich.V.Kirillova.Haukka....da.J..Pombeiro.Angew.Chem.Int.Ed.44,4345(2005)"},{"key":"ref431","doi-asserted-by":"publisher","author":"Hartman","DOI":"10.1002\/(SICI)1521-3773(20000303)39:5&lt;888::AID-ANIE888&gt;3.0.CO;2-...Angew.Chem.,Int.Ed.39,888(2000)"},{"key":"ref131","doi-asserted-by":"publisher","author":"Kirillova","journal-title":"Am Chem Soc","DOI":"10.1021\/ja072531u,(e).........da...da...Pombeiro.J....129,10531(2007)"},{"key":"ref181","article-title":"a University New York","author":"Whyman","year":"2001","journal-title":"Applied Organometallic Chemistry Catalysis"},{"key":"ref201","doi-asserted-by":"publisher","journal-title":"Nature","DOI":"10.1038\/4371098aM.Haruta.4371098(2005)"},{"key":"ref271","doi-asserted-by":"publisher","journal-title":"Mol Catal Chem","DOI":"10.1016\/S1381-1169(02)00196-6.B.Shul'pin.J...A:.189,39(2002)"},{"key":"ref341","doi-asserted-by":"publisher","author":"Silva","DOI":"10.1002\/ejic.200800355,(a)M.V.Kirillova.M.Kirillov...Guedesda.J..Pombeiro.Eur.J.Inorg.Chem.3423(2008)"},{"key":"ref381","doi-asserted-by":"publisher","DOI":"10.1039\/b608790f,(e)D.S.Nesterov.N.Kokozay.V.Dyakonenko.V.Shishkin.Jezierska.Ozarowski.M.Kirillov.N.Kopylovich.J..Pombeiro.Chem.Commun.4605(2006)"},{"key":"ref111","doi-asserted-by":"publisher","author":"Reis","DOI":"10.1002\/anie.200390219,(c)......F.Palavra,J.J..da...J.L.Pombeiro.Angew.Chem.,Int.Ed.42,821(2003)"},{"key":"ref311","doi-asserted-by":"publisher","author":"Frausto","journal-title":"Mol Catal Chem","DOI":"10.1016\/j.molcata.2006.09.049,(b)G.S.Mishra,J.J...J.L.Pombeiro.J...A:.256,59(2007)"},{"key":"ref331","first-page":"3169","article-title":"pin","author":"Suss","year":"1999","journal-title":"Trans"},{"key":"ref301","first-page":"304","article-title":"a","author":"Mishra","year":"2006","journal-title":"Appl Catal"},{"key":"ref01","first-page":"249","article-title":"a","author":"Pettinari","year":"2005","journal-title":"Chem Rev"},{"key":"ref71","doi-asserted-by":"publisher","author":"Alegria","journal-title":"Trans","DOI":"10.1039\/b611209a,(d)............Pombeiro..4954(2006)"},{"key":"ref191","article-title":"In Othmer Encyclopedia of Chemical Technology th ed New York","volume":"13","author":"Mears","year":"2004"},{"key":"ref391","doi-asserted-by":"publisher","author":"Silva","DOI":"10.1002\/adsc.200505216,(f)A..Kirillov.N.Kopylovich..Kirillova.Y.Karabach.Haukka....da.J..Pombeiro.Adv.Synth.Catal.348,159(2006)"},{"key":"ref141","doi-asserted-by":"publisher","author":"Kirillova","journal-title":"Eur","DOI":"10.1002\/chem.200700980,(f).......da...Guedesda...da...Pombeiro.Chem..J.14,1828(2008)"},{"key":"ref31","article-title":"of pyrazolyl borate","author":"Trofimenko","year":"1999","journal-title":"Coordination Chemistry Poly Imperial College"},{"key":"ref151","doi-asserted-by":"publisher","journal-title":"Nature","DOI":"10.1038\/4371243a,(a)R.MokayaM.Poliakoff.4371243(2005)"},{"key":"ref61","first-page":"1979","author":"Silva","year":"2007","journal-title":"Acta Crystallogr"},{"key":"ref371","first-page":"317","author":"Alegria","year":"2007","journal-title":"Appl Catal"},{"key":"ref261","doi-asserted-by":"publisher","author":"Alegria","journal-title":"Mol Catal Chem","DOI":"10.1016\/j.molcata.2008.01.022..Mishra...........da...Pombeiro.J...A:.285,92(2008)"},{"key":"ref351","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2007.11.007,(b)Y.Y.Karabach.M.Kirillov.Haukka.N.Kopylovich.J.L.Pombeiro.J.Inorg.Biochem.102,1190(2008)"},{"key":"ref291","doi-asserted-by":"publisher","journal-title":"Rendus Chimie","DOI":"10.1016\/S1631-0748(03)00021-3,(b)G.B.Shul'pin.Comptes6,163(2003)"},{"key":"ref171","doi-asserted-by":"publisher","journal-title":"Rev","DOI":"10.1021\/cr9411886,(c)A.E.Shilov.B.Shul'pin.Chem..97,2879(1997)"},{"key":"ref421","doi-asserted-by":"publisher","journal-title":"Mol Catal Chem","DOI":"10.1016\/S1381-1169(03)00420-5,(i)M.N.Kopylovich.M.Kirillov.K.Baev.J.L.Pombeiro.J...A:.206,163(2003)"},{"key":"ref101","doi-asserted-by":"publisher","author":"Reis","DOI":"10.1039\/b005513l,(b).....J.J..F.da.J..Pombeiro.Chem.Commun.1845(2000)"},{"key":"ref121","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200505092,(d)A.M.Kirillov.Haukka.V.Kirillova.J.L.Pombeiro.Adv.Synth.Catal.347,1435(2005)"},{"key":"ref51","doi-asserted-by":"publisher","author":"Silva","DOI":"10.1002\/adsc.200700529,(b)...............Pombeiro.Adv.Synth.Catal.350,706(2008)"},{"key":"ref41","doi-asserted-by":"publisher","author":"Wanke","DOI":"10.1021\/ic801254b,(a)..Smole?ski...Guedesda....S....Pombeiro.Inorg.Chem.47,10158(2008)"},{"key":"ref231","doi-asserted-by":"publisher","author":"Kumar","journal-title":"Lett","DOI":"10.1023\/A:1016076526549.S.Mishra..Catal..81,113(2002)"},{"key":"ref11","doi-asserted-by":"publisher","author":"Lawrence","journal-title":"Trans","DOI":"10.1039\/b413121e,(b)H.R.Bigmore....S.Tredget..635(2005)"},{"key":"ref81","doi-asserted-by":"publisher","author":"Alegria","DOI":"10.1016\/j.jorganchem.2004.11.005,(e)............da...Pombeiro.J.Organomet.Chem.690,1947(2005)"},{"key":"ref161","first-page":"211","article-title":"da","author":"Schuchardt","year":"2001","journal-title":"Appl Catal"}],"container-title":["Pure and Applied Chemistry"],"original-title":[],"link":[{"URL":"https:\/\/www.degruyter.com\/view\/journals\/pac\/81\/7\/article-p1217.xml","content-type":"text\/html","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/www.degruyter.com\/downloadpdf\/journals\/pac\/81\/7\/article-p1217.xml","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2021,2,27]],"date-time":"2021-02-27T18:54:49Z","timestamp":1614452089000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.degruyter.com\/document\/doi\/10.1351\/PAC-CON-08-10-08\/html"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,5,31]]},"references-count":43,"journal-issue":{"issue":"7"},"URL":"https:\/\/doi.org\/10.1351\/pac-con-08-10-08","relation":{},"ISSN":["1365-3075","0033-4545"],"issn-type":[{"value":"1365-3075","type":"electronic"},{"value":"0033-4545","type":"print"}],"subject":[],"published":{"date-parts":[[2009,5,31]]}}}