{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T01:09:09Z","timestamp":1760404149348,"version":"3.37.3"},"reference-count":46,"publisher":"Wiley","issue":"9","license":[{"start":{"date-parts":[[2016,1,28]],"date-time":"2016-01-28T00:00:00Z","timestamp":1453939200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"name":"Austrian Science Fund"},{"name":"FWF","award":["P24583-N28"],"award-info":[{"award-number":["P24583-N28"]}]},{"name":"Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","award":["UID\/QUI\/00100\/2013"],"award-info":[{"award-number":["UID\/QUI\/00100\/2013"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angewandte Chemie"],"published-print":{"date-parts":[[2016,2,24]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The synthesis and reactivity of a Co<jats:sup>I<\/jats:sup> pincer complex [Co(<jats:italic>\u03f0<\/jats:italic><jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>CH<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010P(CH)P<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CO)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> featuring an \u03b7<jats:sup>2<\/jats:sup>\u2010 C<jats:sub>aryl<\/jats:sub>\u2212H agostic bond is described. This complex was obtained by protonation of the Co<jats:sup>I<\/jats:sup> complex [Co(PCP<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CO)<jats:sub>2<\/jats:sub>]. The Co<jats:sup>III<\/jats:sup> hydride complex [Co(PCP<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>(H)]<jats:sup>+<\/jats:sup> was obtained upon protonation of [Co(PCP<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>]. Three ways to cleave the agostic C\u2212H bond are presented. First, owing to the acidity of the agostic proton, treatment with pyridine results in facile deprotonation (C\u2212H bond cleavage) and reformation of [Co(PCP<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CO)<jats:sub>2<\/jats:sub>]. Second, C\u2212H bond cleavage is achieved upon exposure of [Co(<jats:italic>\u03f0<\/jats:italic><jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>CH<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010P(CH)P<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CO)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> to oxygen or TEMPO to yield the paramagnetic Co<jats:sup>II<\/jats:sup> PCP complex [Co(PCP<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CO)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup>. Finally, replacement of one CO ligand in [Co(<jats:italic>\u03f0<\/jats:italic><jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>CH<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010P(CH)P<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CO)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> by CN<jats:italic>t<\/jats:italic>Bu promotes the rapid oxidative addition of the agostic \u03b7<jats:sup>2<\/jats:sup>\u2010C<jats:sub>aryl<\/jats:sub>\u2212H bond to give two isomeric hydride complexes of the type [Co(PCP<jats:sup>NMe<\/jats:sup>\u2010<jats:italic>i<\/jats:italic>Pr)(CN<jats:italic>t<\/jats:italic>Bu)(CO)(H)]<jats:sup>+<\/jats:sup>.<\/jats:p>","DOI":"10.1002\/ange.201510145","type":"journal-article","created":{"date-parts":[[2016,1,29]],"date-time":"2016-01-29T02:05:01Z","timestamp":1454033101000},"page":"3097-3100","source":"Crossref","is-referenced-by-count":13,"title":["A Cobalt(I) Pincer Complex with an \u03b7<sup>2<\/sup>\u2010C<sub>aryl<\/sub>\u2212H Agostic Bond: Facile C\u2212H Bond Cleavage through Deprotonation, Radical Abstraction, and Oxidative Addition"],"prefix":"10.1002","volume":"128","author":[{"given":"Sathiyamoorthy","family":"Murugesan","sequence":"first","affiliation":[{"name":"Institute of Applied Synthetic Chemistry Vienna University of Technology  Getreidemarkt 9 1060 Wien Austria"}]},{"given":"Berthold","family":"St\u00f6ger","sequence":"additional","affiliation":[{"name":"Institute of Chemical Technologies and Analytics Vienna University of Technology  Getreidemarkt 9 1060 Wien Austria"}]},{"given":"Ernst","family":"Pittenauer","sequence":"additional","affiliation":[{"name":"Institute of Chemical Technologies and Analytics Vienna University of Technology  Getreidemarkt 9 1060 Wien Austria"}]},{"given":"G\u00fcnter","family":"Allmaier","sequence":"additional","affiliation":[{"name":"Institute of Chemical Technologies and Analytics Vienna University of Technology  Getreidemarkt 9 1060 Wien Austria"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5841-3519","authenticated-orcid":false,"given":"Luis F.","family":"Veiros","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico Universidade de Lisboa  Av. Rovisco Pais No. 1 1049-001 Lisboa Portugal"}]},{"given":"Karl","family":"Kirchner","sequence":"additional","affiliation":[{"name":"Institute of Applied Synthetic Chemistry Vienna University of Technology  Getreidemarkt 9 1060 Wien Austria"}]}],"member":"311","published-online":{"date-parts":[[2016,1,28]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"For recent reviews on C\u2212H activation and functionalization see"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar000209h"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0104330"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900005n"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr300153j"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar800042p"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar200188f"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3cs60020c"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/c1cs15083a"},{"key":"e_1_2_2_10_1","unstructured":"\u00a0"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9411886"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1038\/417507a"},{"key":"e_1_2_2_13_2","first-page":"31","volume":"12","author":"Sakaki S.","year":"2005","journal-title":"Top. Organomet. Chem."},{"key":"e_1_2_2_14_1","unstructured":"For the central role of agostic interactions in C\u2212H activations see"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9502615"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2004.07.034"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja029197g"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic050007n"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1177485"},{"key":"e_1_2_2_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b00069"},{"key":"e_1_2_2_21_1","unstructured":"\u00a0"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja982534u"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/om980960i"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200604357"},{"key":"e_1_2_2_24_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200604357"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/om801147w"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200901526"},{"key":"e_1_2_2_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00037a045"},{"key":"e_1_2_2_28_1","unstructured":"\u00a0"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9710060"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0005001"},{"key":"e_1_2_2_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00022a017"},{"key":"e_1_2_2_32_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2003.11.014"},{"key":"e_1_2_2_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/om000085c"},{"key":"e_1_2_2_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic3006508"},{"key":"e_1_2_2_35_1","unstructured":"Diamagnetic square-planar d8-complexes of CoIare rare in comparison to RhIand IrIspecies. In most cases CoIspecies tend to slip away to the high-spin state or to higher oxidation states like CoIIor CoIII for examples see:"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200527y"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200300569"},{"key":"e_1_2_2_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/om5007769"},{"key":"e_1_2_2_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/om800248e"},{"key":"e_1_2_2_40_1","unstructured":"\u00a0"},{"key":"e_1_2_2_41_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(68)88057-3"},{"key":"e_1_2_2_42_2","unstructured":"Wiberg indices are electronic parameters related with the electron density between two atoms which serve as bond strength indicators. They can be obtained from a Natural Population Analysis."},{"key":"e_1_2_2_43_1","unstructured":"This complex was prepared by treatment of [Co(PCPMe-iPr)(\u03b72-BH4)] (ref.\u2005[17]) with 2\u2005equivs of CNtBu."},{"key":"e_1_2_2_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.5b00075"},{"key":"e_1_2_2_45_1","unstructured":"CCDC\u20051049854 1049856 and 1049857contain the supplementary crystallographic data for this paper. These data are provided free of charge byThe Cambridge Crystallographic Data Centre."}],"container-title":["Angewandte Chemie"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fange.201510145","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fange.201510145","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ange.201510145","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,14]],"date-time":"2023-09-14T01:29:15Z","timestamp":1694654955000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/ange.201510145"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2016,1,28]]},"references-count":46,"journal-issue":{"issue":"9","published-print":{"date-parts":[[2016,2,24]]}},"alternative-id":["10.1002\/ange.201510145"],"URL":"https:\/\/doi.org\/10.1002\/ange.201510145","archive":["Portico"],"relation":{},"ISSN":["0044-8249","1521-3757"],"issn-type":[{"type":"print","value":"0044-8249"},{"type":"electronic","value":"1521-3757"}],"subject":[],"published":{"date-parts":[[2016,1,28]]}}}