{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T06:14:30Z","timestamp":1790662470768,"version":"4.1.0"},"reference-count":69,"publisher":"Wiley","issue":"17","license":[{"start":{"date-parts":[[2009,3,5]],"date-time":"2009-03-05T00:00:00Z","timestamp":1236211200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2009,4,20]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:bold>Do the hydrogen shuffle!<\/jats:bold> DFT calculations and experiments reveal low\u2010barrier multistep pathways for hydrogen\u2010atom transfer from organic radicals to [Co<jats:sup>II<\/jats:sup>(por)]<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold> to form [Co(H)(por)], and for the radical pathway leading to net olefin insertion into the Co\uf8ffH bond of [Co(H)(por)] (see scheme). The results suggest that hydrogen\u2010atom\u2010transfer pathways could be important in numerous addition reactions of M\uf8ffH complexes with unsaturated substrates.<jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" mimetype=\"image\/gif\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic\/mcontent.gif\"><jats:alt-text>magnified image<\/jats:alt-text><\/jats:graphic><\/jats:boxed-text><\/jats:p><jats:p>The mechanisms for hydrogen\u2010atom transfer from the cyanoisopropyl radical <jats:bold><jats:sup>.<\/jats:sup><\/jats:bold>C(CH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>CN to [Co<jats:sup>II<\/jats:sup>(por)]<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold> (yielding [Co<jats:sup>III<\/jats:sup>(H)(por)] and CH<jats:sub>2<\/jats:sub>\uf8feC(CH<jats:sub>3<\/jats:sub>)(CN); por=porphyrinato) and the insertion of vinyl acetate (CH<jats:sub>2<\/jats:sub>\uf8feCHOAc) into the Co\uf8ffH bond of [Co(H)(por)] (giving [Co<jats:sup>III<\/jats:sup>{CH(OAc)CH<jats:sub>3<\/jats:sub>}(por)]) were investigated by DFT calculations. The results are compared with experimental data. These reactions are relevant to catalytic chain transfer (CCT) in radical polymerization of olefins mediated by [Co<jats:sup>II<\/jats:sup>(por)]<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold>, the formation and homolysis of organo\u2010cobalt complexes that mediate living radical polymerization of vinyl acetate, and cobalt\u2010mediated hydrogenation of olefins. Hydrogen transfer from <jats:bold><jats:sup>.<\/jats:sup><\/jats:bold>C(CH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>CN to [Co<jats:sup>II<\/jats:sup>(por)]<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold> proceeds via a single transition state that has structural features resembling the products [Co(H)(por)] and CH<jats:sub>2<\/jats:sub>\uf8feC(CH<jats:sub>3<\/jats:sub>)CN. The separated radicals approach to form a close\u2010contact radical pair and then pass through the transition state for hydrogen\u2010atom transfer to form [Co<jats:sup>III<\/jats:sup>(H)(por)] and CH<jats:sub>2<\/jats:sub>\uf8feC(CH<jats:sub>3<\/jats:sub>)CN. This process provides a very low overall barrier for the hydrogen\u2010atom transfer reaction (\u0394<jats:italic>G<jats:sup>\u2260<\/jats:sup><\/jats:italic>= +3.8\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>). The reverse reaction corresponding to the addition of [Co(H)(por)] to CH<jats:sub>2<\/jats:sub>\uf8feC(CH<jats:sub>3<\/jats:sub>)CN has a low barrier (\u0394<jats:italic>G<jats:sup>\u2260<\/jats:sup><\/jats:italic>=+8.9\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) as well. Insertion of vinyl acetate into the Co\uf8ffH bond of [Co<jats:sup>III<\/jats:sup>(H)(por)] also proceeds over a low barrier (\u0394<jats:italic>G<jats:sup>\u2260<\/jats:sup><\/jats:italic>= +11.4\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) hydrogen\u2010transfer step from [Co<jats:sup>III<\/jats:sup>(H)(por)] to a carbon atom of the alkene to produce a close\u2010contact radical pair. Dissociation of the radical pair, reorientation, and radical\u2013radical coupling to form an organo\u2010cobalt complex are the culminating steps in the net insertion of an olefin into the Co\uf8ffH bond. The computed energies obtained for the hydrogen\u2010atom transfer reactions from <jats:bold><jats:sup>.<\/jats:sup><\/jats:bold>C(CH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>CN to [Co<jats:sup>II<\/jats:sup>(por)]<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold> and from [Co(H)(por)] to olefins, as well as the organo\u2010cobalt bond homolysis energies correspond well with the experimental observations. The mechanism of alkene insertion into the Co\uf8ffH bond of [Co<jats:sup>III<\/jats:sup>(H)(por)] is of general interest, because the species does not contain any <jats:italic>cis<\/jats:italic>\u2010vacant sites to the hydride and the usual migratory insertion pathway is not available. The low barrier predicted here for the multistep insertion process suggests that (depending on the bond strengths) even for systems that do have a <jats:italic>cis<\/jats:italic>\u2010vacant site, the radical\u2010type insertion might compete with classical migratory insertion.<\/jats:p>","DOI":"10.1002\/chem.200802022","type":"journal-article","created":{"date-parts":[[2009,3,5]],"date-time":"2009-03-05T08:17:35Z","timestamp":1236241055000},"page":"4312-4320","source":"Crossref","is-referenced-by-count":69,"title":["Hydrogen\u2010Atom Transfer in Reactions of Organic Radicals with [Co<sup>II<\/sup>(por)]<sup>.<\/sup> (por=Porphyrinato) and in Subsequent Addition of [Co(H)(por)] to Olefins"],"prefix":"10.1002","volume":"15","author":[{"given":"Bas","family":"de\u2005Bruin","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wojciech\u2005I.","family":"Dzik","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shan","family":"Li","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bradford\u2005B.","family":"Wayland","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,4,15]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma061643n"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00096a080"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma070836n"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma702500b"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja046936f"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9901236"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00036a029"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma061574c"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00366a046"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja804010h"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma9914523"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma035612t"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja010998d"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma034046z"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2008.01.014"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma0618833"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200461333"},{"key":"e_1_2_6_17_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200461333"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/marc.200500645"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200701867"},{"key":"e_1_2_6_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200701867"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00095a029"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja960002c"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp027566p"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20454"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp021706d"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0377551"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/b700096k"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0578451"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0507565"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200400850"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic001457c"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja993375x"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1097-461X(2000)77:1<316::AID-QUA30>3.0.CO;2-5"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja001259k"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50159a027"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00822a017"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00749a076"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1480872"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0603058"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(97)05840-4"},{"key":"e_1_2_6_40_2","unstructured":"With the applied static DFT methods there exist no methods to find transition states that exist only in the free\u2010energy landscape but not in the electronic\u2010energy landscape. 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