{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T21:13:58Z","timestamp":1788383638214,"version":"build-2803163510"},"reference-count":74,"publisher":"American Chemical Society (ACS)","issue":"15","license":[{"start":{"date-parts":[[2016,1,29]],"date-time":"2016-01-29T00:00:00Z","timestamp":1454025600000},"content-version":"vor","delay-in-days":935,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_termsofuse.html"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2013,8,5]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The complex [Cp*RuCl(iPr2PNHPy)] (1) reacts with 1-alkynes HC\u2261CR (R = COOMe, C6H4CF3) in dichloromethane furnishing the corresponding vinylidene complexes [Cp*Ru\u2550C\u2550CHR(iPr2PNHPy)]Cl (R = COOMe (2a-Cl), C6H4CF3 (2b-Cl)), whereas reaction of 1 with NaBPh4 in MeOH followed by addition of HC\u2261CR (R = COOMe, C6H4CF3) yields the metastable \u03c0-alkyne complexes [Cp*Ru(\u03b72-HC\u2261CR)(iPr2PNHPy)][BPh4] (R = COOMe (3a-BPh4), C6H4CF3(3b-BPh4)). The transformation of 3a-BPh4\/3b-BPh4 into their respective vinylidene isomers in dichloromethane is very slow and requires hours to its completion. However, this process is accelerated by addition of LiCl in methanol solution. Reaction of 1 with HC\u2261CR (R = COOMe, C6H4CF3) in MeOH goes through the intermediacy of the \u03c0-alkyne complexes [Cp*Ru(\u03b72-HC\u2261CR)(iPr2PNHPy)]Cl (R = COOMe (3a-Cl), C6H4CF3 (3b-Cl)), which rearrange to vinylidenes in minutes, i.e., much faster than their counterparts containing the [BPh4]\u2212 anion. The kinetics of these isomerizations has been studied in solution by NMR. With the help of DFT studies, these observations have been interpreted in terms of chloride- and methanol-assisted hydrogen migrations. Calculations suggest participation of a hydrido\u2013alkynyl intermediate in the process, in which the hydrogen atom can be transferred from the metal to the \u03b2-carbon by means of species with weak basic character acting as proton shuttles.<\/jats:p>","DOI":"10.1021\/ic401119p","type":"journal-article","created":{"date-parts":[[2013,7,8]],"date-time":"2013-07-08T15:08:50Z","timestamp":1373296130000},"page":"8919-8932","source":"Crossref","is-referenced-by-count":39,"title":["Counteranion\nand Solvent Assistance in Ruthenium-Mediated Alkyne to Vinylidene\nIsomerizations"],"prefix":"10.1021","volume":"52","author":[{"given":"Manuel","family":"Jime\u0301nez-Tenorio","sequence":"first","affiliation":[{"name":"Universidad de Ca\u0301diz Departamento de Ciencia de los Materiales e Ingenieri\u0301a Metalu\u0301rgica y Qui\u0301mica Inorga\u0301nica, Facultad de Ciencias, , 11510 Puerto Real, Ca\u0301diz, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"M. Carmen","family":"Puerta","sequence":"additional","affiliation":[{"name":"Universidad de Ca\u0301diz Departamento de Ciencia de los Materiales e Ingenieri\u0301a Metalu\u0301rgica y Qui\u0301mica Inorga\u0301nica, Facultad de Ciencias, , 11510 Puerto Real, Ca\u0301diz, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pedro","family":"Valerga","sequence":"additional","affiliation":[{"name":"Universidad de Ca\u0301diz Departamento de Ciencia de los Materiales e Ingenieri\u0301a Metalu\u0301rgica y Qui\u0301mica Inorga\u0301nica, Facultad de Ciencias, , 11510 Puerto Real, Ca\u0301diz, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Manuel A.","family":"Ortun\u0303o","sequence":"additional","affiliation":[{"name":"Universitat Auto\u0300noma de Barcelona Departament de Qui\u0301mica, , 08193 Cerdanyola del Valle\u0300s, Barcelona, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gregori","family":"Ujaque","sequence":"additional","affiliation":[{"name":"Universitat Auto\u0300noma de Barcelona Departament de Qui\u0301mica, , 08193 Cerdanyola del Valle\u0300s, Barcelona, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Agusti\u0301","family":"Lledo\u0301s","sequence":"additional","affiliation":[{"name":"Universitat Auto\u0300noma de Barcelona Departament de Qui\u0301mica, , 08193 Cerdanyola del Valle\u0300s, Barcelona, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2013,7,8]]},"reference":[{"key":"2026090216114152200_cit1a","doi-asserted-by":"crossref","first-page":"255","DOI":"10.1016\/0022-328X(90)85231-M","volume":"382","author":"Ho\u0308hn","year":"1990","journal-title":"J. Organomet. Chem."},{"key":"2026090216114152200_cit1b","doi-asserted-by":"crossref","first-page":"4156","DOI":"10.1021\/om00060a036","volume":"11","author":"Rappert","year":"1992","journal-title":"Organometallics"},{"key":"2026090216114152200_cit2a","doi-asserted-by":"crossref","first-page":"165","DOI":"10.1039\/C39890000165","author":"Bullock","year":"1989","journal-title":"J. Chem. Soc., Chem. Commun."},{"key":"2026090216114152200_cit2b","doi-asserted-by":"crossref","first-page":"5518","DOI":"10.1021\/ja00040a005","volume":"114","author":"Lomprey","year":"1992","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit3","doi-asserted-by":"crossref","first-page":"6529","DOI":"10.1021\/ja9701220","volume":"119","author":"de los Ri\u0301os","year":"1997","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit4","doi-asserted-by":"crossref","first-page":"977","DOI":"10.1016\/S0010-8545(99)00166-6","volume":"193\u2013195","author":"Puerta","year":"1999","journal-title":"Coord. Chem. Rev."},{"key":"2026090216114152200_cit5","doi-asserted-by":"crossref","first-page":"1749","DOI":"10.1021\/om990957e","volume":"19","author":"Garci\u0301a-Yebra","year":"2000","journal-title":"Organometallics"},{"key":"2026090216114152200_cit6","doi-asserted-by":"crossref","first-page":"3311","DOI":"10.1021\/ja0291181","volume":"125","author":"Bustelo","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit7a","doi-asserted-by":"crossref","first-page":"4092","DOI":"10.1016\/j.jorganchem.2004.05.052","volume":"684","author":"Wakatsuki","year":"2004","journal-title":"J. Organomet. Chem."},{"key":"2026090216114152200_cit7b","doi-asserted-by":"crossref","first-page":"11917","DOI":"10.1021\/ja0119292","volume":"123","author":"Tokunaga","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit7c","doi-asserted-by":"crossref","first-page":"360","DOI":"10.1021\/ja962732q","volume":"119","author":"Wakatsuki","year":"1997","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit7d","doi-asserted-by":"crossref","first-page":"8105","DOI":"10.1021\/ja00097a017","volume":"116","author":"Wakatsuki","year":"1994","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit8","doi-asserted-by":"crossref","first-page":"2715","DOI":"10.1021\/om010943k","volume":"21","author":"De Angelis","year":"2002","journal-title":"Organometallics"},{"key":"2026090216114152200_cit9","doi-asserted-by":"crossref","first-page":"5944","DOI":"10.1021\/om020723m","volume":"21","author":"De Angelis","year":"2002","journal-title":"Organometallics"},{"key":"2026090216114152200_cit10","doi-asserted-by":"crossref","first-page":"3225","DOI":"10.1039\/b408452g","author":"De Angelis","year":"2004","journal-title":"Dalton\nTrans."},{"key":"2026090216114152200_cit11","doi-asserted-by":"crossref","first-page":"5285","DOI":"10.1021\/om7003964","volume":"26","author":"De Angelis","year":"2007","journal-title":"Organometallics"},{"key":"2026090216114152200_cit12","doi-asserted-by":"crossref","first-page":"3697","DOI":"10.1021\/om00056a048","volume":"10","author":"Bianchini","year":"1991","journal-title":"Organometallics"},{"key":"2026090216114152200_cit13","doi-asserted-by":"crossref","first-page":"2798","DOI":"10.1021\/ja058736p","volume":"128","author":"Grotjahn","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit14","doi-asserted-by":"crossref","first-page":"3385","DOI":"10.1021\/om700355r","volume":"26","author":"Grotjahn","year":"2007","journal-title":"Organometallics"},{"key":"2026090216114152200_cit15","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1142\/S0219633605001325","volume":"4","author":"Suresh","year":"2005","journal-title":"J. Theor. Comput. Chem."},{"key":"2026090216114152200_cit16","doi-asserted-by":"crossref","first-page":"4325","DOI":"10.1021\/om8001137","volume":"27","author":"Vastine","year":"2008","journal-title":"Organometallics"},{"key":"2026090216114152200_cit17","doi-asserted-by":"crossref","first-page":"4552","DOI":"10.1039\/b806358c","author":"Cowley","year":"2008","journal-title":"Dalton Trans."},{"key":"2026090216114152200_cit18","doi-asserted-by":"crossref","first-page":"1703","DOI":"10.1016\/j.ccr.2004.05.031","volume":"248","author":"Katayama","year":"2004","journal-title":"Coord. Chem. Rev."},{"key":"2026090216114152200_cit19","doi-asserted-by":"crossref","first-page":"2176","DOI":"10.1002\/anie.200501391","volume":"45","author":"Bruneau","year":"2006","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090216114152200_cit20","first-page":"7147","volume":"11","author":"Grotjahn","year":"2005","journal-title":"Chem.\u2500Eur. J."},{"key":"2026090216114152200_cit21","doi-asserted-by":"crossref","first-page":"6497","DOI":"10.1039\/b809274e","author":"Grotjahn","year":"2008","journal-title":"Dalton Trans."},{"key":"2026090216114152200_cit22a","doi-asserted-by":"crossref","first-page":"4014","DOI":"10.1021\/om200273v","volume":"30","author":"Singh","year":"2011","journal-title":"Organometallics"},{"key":"2026090216114152200_cit22b","doi-asserted-by":"crossref","first-page":"1740","DOI":"10.1021\/om100084x","volume":"29","author":"de los Ri\u0301os","year":"2010","journal-title":"Organometallics"},{"key":"2026090216114152200_cit22c","doi-asserted-by":"crossref","first-page":"17746","DOI":"10.1021\/ja308018b","volume":"134","author":"Otsuka","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit23a","doi-asserted-by":"crossref","first-page":"2391","DOI":"10.1002\/1099-0682(200109)2001:9<2391::AID-EJIC2391>3.0.CO;2-Z","author":"Bustelo","year":"2001","journal-title":"Eur. J. Inorg. Chem."},{"key":"2026090216114152200_cit23b","doi-asserted-by":"crossref","first-page":"2001","DOI":"10.1021\/om020940n","volume":"22","author":"Aneetha","year":"2003","journal-title":"Organometallics"},{"key":"2026090216114152200_cit24","doi-asserted-by":"crossref","first-page":"6603","DOI":"10.1021\/om9007295","volume":"28","author":"Creati","year":"2009","journal-title":"Organometallics"},{"key":"2026090216114152200_cit25a","doi-asserted-by":"crossref","first-page":"2039","DOI":"10.1021\/cr0300439","volume":"105","author":"Macchioni","year":"2005","journal-title":"Chem. Rev."},{"key":"2026090216114152200_cit25b","doi-asserted-by":"crossref","first-page":"2319","DOI":"10.1002\/ejic.200900151","author":"Clot","year":"2009","journal-title":"Eur.\nJ. Inorg. Chem."},{"key":"2026090216114152200_cit26","doi-asserted-by":"crossref","first-page":"6608","DOI":"10.1021\/ja070939l","volume":"129","author":"Basallote","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit27","doi-asserted-by":"crossref","first-page":"853","DOI":"10.1021\/ja073578i","volume":"130","author":"Kova\u0301cs","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit28a","doi-asserted-by":"crossref","first-page":"16299","DOI":"10.1021\/ja055317j","volume":"127","author":"Appelhans","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit28b","doi-asserted-by":"crossref","first-page":"6940","DOI":"10.1021\/ja802144t","volume":"130","author":"Xia","year":"2008","journal-title":"J. Am.\nChem. Soc."},{"key":"2026090216114152200_cit28c","doi-asserted-by":"crossref","first-page":"5820","DOI":"10.1039\/b904967c","author":"Boutadla","year":"2009","journal-title":"Dalton Trans."},{"key":"2026090216114152200_cit29","doi-asserted-by":"crossref","first-page":"1767","DOI":"10.1002\/ejic.200901162","author":"Maci\u0301as-Arce","year":"2010","journal-title":"Eur. J. Inorg. Chem."},{"key":"2026090216114152200_cit30","doi-asserted-by":"crossref","first-page":"20","DOI":"10.1021\/ja0774616","volume":"130","author":"Grotjahn","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit31","doi-asserted-by":"crossref","first-page":"4868","DOI":"10.1021\/ic200547k","volume":"50","author":"Di\u0301ez","year":"2011","journal-title":"Inorg. Chem."},{"key":"2026090216114152200_cit32","doi-asserted-by":"crossref","first-page":"726","DOI":"10.1021\/om101013j","volume":"30","author":"Hyder","year":"2011","journal-title":"Organometallics"},{"key":"2026090216114152200_cit33","doi-asserted-by":"crossref","first-page":"4741","DOI":"10.1002\/ejoc.200500411","author":"Kotha","year":"2005","journal-title":"Eur. J. Inorg. Chem."},{"key":"2026090216114152200_cit34","doi-asserted-by":"crossref","first-page":"379","DOI":"10.1021\/om00104a016","volume":"8","author":"Bryndza","year":"1989","journal-title":"Organometallics"},{"key":"2026090216114152200_cit38","doi-asserted-by":"crossref","first-page":"10432","DOI":"10.1039\/c0dt00431f","volume":"39","author":"Johnson","year":"2010","journal-title":"Dalton Trans."},{"key":"2026090216114152200_cit39","doi-asserted-by":"crossref","first-page":"9709","DOI":"10.1021\/jp802665d","volume":"112","author":"Vyacheslav","year":"2008","journal-title":"J. Phys. Chem. B"},{"key":"2026090216114152200_cit40a","doi-asserted-by":"crossref","first-page":"5121","DOI":"10.1021\/om100326z","volume":"29","author":"Kova\u0301cs","year":"2010","journal-title":"Organometallics"},{"key":"2026090216114152200_cit40b","doi-asserted-by":"crossref","first-page":"2087","DOI":"10.1021\/cs300369j","volume":"2","author":"Di\u0301ez","year":"2012","journal-title":"ACS Catal."},{"key":"2026090216114152200_cit42a","doi-asserted-by":"crossref","first-page":"2237","DOI":"10.1021\/ol9004646","volume":"11","author":"Paton","year":"2009","journal-title":"Org. Lett."},{"key":"2026090216114152200_cit42b","doi-asserted-by":"crossref","first-page":"3129","DOI":"10.1021\/om801115a","volume":"28","author":"Zhang","year":"2009","journal-title":"Organometallics"},{"key":"2026090216114152200_cit42c","doi-asserted-by":"crossref","first-page":"3252","DOI":"10.1021\/om100063v","volume":"29","author":"Kova\u0301cs","year":"2010","journal-title":"Organometallics"},{"key":"2026090216114152200_cit42d","doi-asserted-by":"crossref","first-page":"5919","DOI":"10.1021\/om1007192","volume":"29","author":"Kova\u0301cs","year":"2010","journal-title":"Organometallics"},{"key":"2026090216114152200_cit42e","doi-asserted-by":"crossref","first-page":"16882","DOI":"10.1021\/ja308038z","volume":"134","author":"Ariafard","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit43","doi-asserted-by":"crossref","first-page":"943","DOI":"10.1021\/om980519s","volume":"18","author":"Steinmetz","year":"1999","journal-title":"Organometallics"},{"key":"2026090216114152200_cit44a","doi-asserted-by":"crossref","first-page":"3865","DOI":"10.1103\/PhysRevLett.77.3865","volume":"77","author":"Perdew","year":"1996","journal-title":"Phys. Rev. Lett."},{"key":"2026090216114152200_cit44b","doi-asserted-by":"crossref","first-page":"9982","DOI":"10.1063\/1.472933","volume":"105","author":"Perdew","year":"1996","journal-title":"J. Chem. Phys."},{"key":"2026090216114152200_cit45","volume-title":"Gaussian 09","author":"Frisch","year":"2009"},{"key":"2026090216114152200_cit46a","doi-asserted-by":"crossref","first-page":"709","DOI":"10.1021\/jp054449w","volume":"110","author":"Quintal","year":"2006","journal-title":"J. Phys. Chem. A"},{"key":"2026090216114152200_cit46b","doi-asserted-by":"crossref","first-page":"2234","DOI":"10.1021\/ct700178y","volume":"3","author":"Waller","year":"2007","journal-title":"J. Chem. Theory Comput."},{"key":"2026090216114152200_cit47","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"key":"2026090216114152200_cit48","doi-asserted-by":"crossref","first-page":"395","DOI":"10.1021\/ct900639j","volume":"6","author":"Wheeler","year":"2010","journal-title":"J. Chem. Theory Comput."},{"key":"2026090216114152200_cit49","doi-asserted-by":"crossref","first-page":"123","DOI":"10.1007\/BF01114537","volume":"77","author":"Andrae","year":"1990","journal-title":"Theor. Chim. Acta"},{"key":"2026090216114152200_cit50","doi-asserted-by":"crossref","first-page":"111","DOI":"10.1016\/0009-2614(93)80086-5","volume":"208","author":"Ehlers","year":"1993","journal-title":"Chem. Phys. Lett."},{"key":"2026090216114152200_cit51","doi-asserted-by":"crossref","first-page":"2257","DOI":"10.1063\/1.1677527","volume":"56","author":"Hehre","year":"1972","journal-title":"J. Chem. Phys."},{"key":"2026090216114152200_cit52","doi-asserted-by":"crossref","first-page":"3654","DOI":"10.1063\/1.444267","volume":"77","author":"Francl","year":"1982","journal-title":"J. Chem. Phys."},{"key":"2026090216114152200_cit53","doi-asserted-by":"crossref","first-page":"294","DOI":"10.1002\/jcc.540040303","volume":"4","author":"Clark","year":"1983","journal-title":"J. Comput. Chem."},{"key":"2026090216114152200_cit54","doi-asserted-by":"crossref","first-page":"6378","DOI":"10.1021\/jp810292n","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"2026090216114152200_cit55a","doi-asserted-by":"crossref","first-page":"397","DOI":"10.1051\/jphysrad:01937008010039700","volume":"8","author":"London","year":"1937","journal-title":"J. Phys. Radium"},{"key":"2026090216114152200_cit55b","doi-asserted-by":"crossref","first-page":"1028","DOI":"10.1103\/PhysRev.126.1028","volume":"126","author":"McWeeny","year":"1962","journal-title":"Phys. Rev."},{"key":"2026090216114152200_cit55c","doi-asserted-by":"crossref","first-page":"789","DOI":"10.1080\/00268977400100711","volume":"27","author":"Ditchfield","year":"1974","journal-title":"Mol. Phys."},{"key":"2026090216114152200_cit55d","doi-asserted-by":"crossref","first-page":"8251","DOI":"10.1021\/ja00179a005","volume":"112","author":"Wolinski","year":"1990","journal-title":"J. Am. Chem. Soc."},{"key":"2026090216114152200_cit55e","doi-asserted-by":"crossref","first-page":"5497","DOI":"10.1063\/1.471789","volume":"104","author":"Cheeseman","year":"1996","journal-title":"J. Chem. Phys."},{"key":"2026090216114152200_cit56","volume-title":"The IGLO-Method: Ab Initio Calculation and Interpretation\nof NMR Chemical Shifts and Magnetic Susceptibilities","author":"Kutzelnigg","year":"1990"}],"container-title":["Inorganic\nChemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ic401119p","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/inocaj\/article-pdf\/52\/15\/8919\/15880946\/ic401119p.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/inocaj\/article-pdf\/52\/15\/8919\/15880946\/ic401119p.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T20:15:34Z","timestamp":1788380134000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/inocaj\/article\/52\/15\/8919\/1490379\/Counteranion-and-Solvent-Assistance-in-Ruthenium"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2013,7,8]]},"references-count":74,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2013,7,8]]},"published-print":{"date-parts":[[2013,8,5]]}},"URL":"https:\/\/doi.org\/10.1021\/ic401119p","relation":{},"ISSN":["0020-1669","1520-510X"],"issn-type":[{"value":"0020-1669","type":"print"},{"value":"1520-510X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2013,7,8]]}}}