{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,15]],"date-time":"2026-07-15T23:31:43Z","timestamp":1784158303978,"version":"3.55.0"},"reference-count":80,"publisher":"Wiley","issue":"23","license":[{"start":{"date-parts":[[2009,4,28]],"date-time":"2009-04-28T00:00:00Z","timestamp":1240876800000},"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":[[2009,6,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:bold>Do the splits!<\/jats:bold> Metalation of [36]octaphyrin (<jats:bold>1<\/jats:bold>) and the metathesis\u2010like splitting behavior of <jats:bold>1<\/jats:bold>\u2013metal complexes were examined both experimentally and theoretically. Complexes <jats:bold>1<\/jats:bold>\u2013CuCu and <jats:bold>1<\/jats:bold>\u2013CoCu underwent quantitative splitting reactions into two metalloporphyrins, whereas <jats:bold>1<\/jats:bold>\u2013Cu, <jats:bold>1<\/jats:bold>\u2013Co, and <jats:bold>1<\/jats:bold>\u2013ZnZn did not show such reactivity.<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><jats:italic>meso<\/jats:italic>\u2010Octakis(pentafluorophenyl)\u2010substituted [36]octaphyrin(1.1.1.1.1.1.1.1) (<jats:bold>1<\/jats:bold>) is a figure\u2010of\u2010eight nonaromatic macrocycle that serves as a unique platform to induce a metathesis\u2010like splitting reaction upon bis\u2010Cu<jats:sup>II<\/jats:sup> metalation. To get a better understanding of this splitting reaction, we examined the metalation of <jats:bold>1<\/jats:bold> with several metal ions. In contrast with the smooth and quantitative splitting reaction of bis\u2010Cu<jats:sup>II<\/jats:sup> complex <jats:bold>1<\/jats:bold>\u2013CuCu, free\u2010base <jats:bold>1<\/jats:bold>, mono\u2010Cu<jats:sup>II<\/jats:sup> complex <jats:bold>1<\/jats:bold>\u2013Cu, and bis\u2010Zn<jats:sup>II<\/jats:sup> complex <jats:bold>1<\/jats:bold>\u2013ZnZn do not undergo the splitting reaction. Mono\u2010Co<jats:sup>II<\/jats:sup> complex <jats:bold>1<\/jats:bold>\u2013Co was selectively produced from metalation with the Co<jats:sup>II<\/jats:sup> ion, from which hybrid complex <jats:bold>1<\/jats:bold>\u2013CoCu was synthesized. The hybrid complex <jats:bold>1<\/jats:bold>\u2013CoCu undergoes the splitting reaction to give <jats:bold>2<\/jats:bold>\u2013Co and <jats:bold>2<\/jats:bold>\u2013Cu quantitatively. Activation parameters of the splitting reactions were determined: <jats:italic>E<\/jats:italic><jats:sub>a<\/jats:sub>=104\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup>, \u0394<jats:italic>H<\/jats:italic><jats:sup>\u2260<\/jats:sup>=101\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup>, \u0394<jats:italic>S<\/jats:italic><jats:sup>\u2260<\/jats:sup>=\u221225.0\u2005J\u2009mol<jats:sup>\u22121<\/jats:sup>\u2009K<jats:sup>\u22121<\/jats:sup>, and \u0394<jats:italic>V<\/jats:italic><jats:sup>\u2260<\/jats:sup>=18\u2005cm<jats:sup>3<\/jats:sup>\u2009mol<jats:sup>\u22121<\/jats:sup> for <jats:bold>1<\/jats:bold>\u2013CuCu and <jats:italic>E<\/jats:italic><jats:sub>a<\/jats:sub>=105\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup>, \u0394<jats:italic>H<\/jats:italic><jats:sup>\u2260<\/jats:sup>=102\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup>, and \u0394<jats:italic>S<\/jats:italic><jats:sup>\u2260<\/jats:sup>=\u221229.9\u2005J\u2009mol<jats:sup>\u22121<\/jats:sup>\u2009K<jats:sup>\u22121<\/jats:sup> for <jats:bold>1<\/jats:bold>\u2013CoCu. A marked difference between the splitting reaction reactivity of <jats:bold>1<\/jats:bold>\u2013CuCu and <jats:bold>1<\/jats:bold>\u2013ZnZn has been examined by DFT calculations at the B3LYP\/631SDD\/\/B3LYP\/LANL2DZ level, which revealed that the reaction proceeds through a stepwise route involving initial C1\uf8ffC20 bond formation to give <jats:bold>INT1<\/jats:bold> as the rate\u2010determining step and subsequent C21\uf8ffC40 bond formation to give a spirocyclobutane intermediate (<jats:bold>INT2<\/jats:bold>), followed by a radical reverse cycloaddition reaction to give two metalloporphyrins. Inherent instability of <jats:bold>1<\/jats:bold>\u2013CuCu, which may arise from its strongly distorted structure, was indicated to be a main factor in the smooth splitting reaction. Finally, a new bis\u2010Pd<jats:sup>II<\/jats:sup> complex (<jats:bold>5<\/jats:bold>\u2013PdPd) was isolated in the metalation of <jats:bold>1<\/jats:bold> with Pd(OAc)<jats:sub>2<\/jats:sub> in a 9:1 mixture of 2,2,2\u2010trifluoroethanol and methanol as a manifestation of the transannular electronic interaction in metalated octaphyrin complexes. Collectively, these results underscore the importance of the transannular electronic interactions that are enhanced by metalation, depending upon the coordinated metal ions.<\/jats:p>","DOI":"10.1002\/chem.200900454","type":"journal-article","created":{"date-parts":[[2009,4,28]],"date-time":"2009-04-28T14:11:46Z","timestamp":1240927906000},"page":"5674-5685","source":"Crossref","is-referenced-by-count":41,"title":["Metathesis\u2010like Splitting Reactions of Metallated [36]Octaphyrins(1.1.1.1.1.1.1.1): Experimental and Computational Investigations"],"prefix":"10.1002","volume":"15","author":[{"given":"Yasuo","family":"Tanaka","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hiroshi","family":"Shinokubo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yosuke","family":"Yoshimura","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Atsuhiro","family":"Osuka","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,5,26]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19951071704"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199517951"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr950078b"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200200561"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200200561"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/B200525P"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar020284n"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200501097"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700091k"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19941061429"},{"key":"e_1_2_6_10_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199415091"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.19950010110"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19951072211"},{"key":"e_1_2_6_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199525111"},{"key":"e_1_2_6_13_2","doi-asserted-by":"crossref","first-page":"2709","DOI":"10.1002\/ange.19951072212","volume":"107","author":"Br\u00f6ring M.","year":"1995","journal-title":"Angew. 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thus ln\u2009kp=ln\u2009k0\u2212\u0394V\u2260p\/RT."},{"key":"e_1_2_6_55_2","unstructured":"\u00a0"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)89474-0"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00959a052"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr030092l"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0505425"},{"key":"e_1_2_6_60_2","unstructured":"\u00a0"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature02224"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600215"},{"key":"e_1_2_6_63_2","unstructured":"In the crystal of5\u2013PdPd twon\u2010heptane molecules were severely disordered. 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