{"created":"2023-06-26T11:01:49.227539+00:00","id":2576,"links":{},"metadata":{"_buckets":{"deposit":"9dbd7743-f496-452c-b10c-bfb0b6915db2"},"_deposit":{"created_by":30,"id":"2576","owners":[30],"pid":{"revision_id":0,"type":"depid","value":"2576"},"status":"published"},"_oai":{"id":"oai:oist.repo.nii.ac.jp:00002576","sets":["6:228"]},"author_link":["16801","16799","16802","16798","16800"],"item_10001_biblio_info_7":{"attribute_name":"Bibliographic Information","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2022-01-31","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"5","bibliographicPageEnd":"2322","bibliographicPageStart":"2311","bibliographicVolumeNumber":"144","bibliographic_titles":[{},{"bibliographic_title":"Journal of the American Chemical Society","bibliographic_titleLang":"en"}]}]},"item_10001_creator_3":{"attribute_name":"Author","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"Xing, Liwen"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Liu, Ji-Ren"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Hong, Xin"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Houk, Kendall N."}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Luscombe, Christine K."}],"nameIdentifiers":[{}]}]},"item_10001_description_5":{"attribute_name":"Abstract","attribute_value_mlt":[{"subitem_description":"The Carothers equation is often used to predict the utility of a small molecule reaction in a polymerization. In this study, we present the mechanistic study of Pd/Ag cocatalyzed cross dehydrogenative coupling (CDC) polymerization to synthesize a donor–acceptor (D–A) polymer of 3,3′-dihexyl-2,2′-bithiophene and 2,2′,3,3′,5,5′,6,6′-octafluorobiphenyl, which go counter to the Carothers equation. It is uncovered that the second chain extension cross-coupling proceeds much more efficiently than the first cross-coupling and the homocoupling side reaction (at least 1 order of magnitude faster) leading to unexpectedly low homocoupling defects and high molecular weight polymers. Kinetic analyses show that C–H bond activation is rate-determining in the first cross-coupling but not in the second cross-coupling. Based on DFT calculations, the high cross-coupling rate in the second cross-coupling was ascribed to the strong Pd-thiophene interaction in the Pd-mediated C–H bond activation transition state, which decreases the energy barrier of the Pd-mediated C–H bond activation. These results have implications beyond polymerizations and can be used to ease the synthesis of a wide range of molecules where C–H bond activation may be the limiting factor.","subitem_description_type":"Other"}]},"item_10001_publisher_8":{"attribute_name":"Publisher","attribute_value_mlt":[{"subitem_publisher":"American Chemical Society"}]},"item_10001_relation_13":{"attribute_name":"PubMedNo.","attribute_value_mlt":[{"subitem_relation_type":"isIdenticalTo","subitem_relation_type_id":{"subitem_relation_type_id_text":"info:pmid/35100507","subitem_relation_type_select":"PMID"}}]},"item_10001_relation_14":{"attribute_name":"DOI","attribute_value_mlt":[{"subitem_relation_type":"isIdenticalTo","subitem_relation_type_id":{"subitem_relation_type_id_text":"info:doi/10.1021/jacs.1c12599","subitem_relation_type_select":"DOI"}}]},"item_10001_relation_17":{"attribute_name":"Related site","attribute_value_mlt":[{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://pubs.acs.org/doi/10.1021/jacs.1c12599","subitem_relation_type_select":"URI"}}]},"item_10001_rights_15":{"attribute_name":"Rights","attribute_value_mlt":[{"subitem_rights":"© 2022 The Authors."},{"subitem_rights":"ACS AuthorChoice with CC-BY-NC-ND. "}]},"item_10001_source_id_9":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":"0002-7863","subitem_source_identifier_type":"ISSN"},{"subitem_source_identifier":"1520-5126","subitem_source_identifier_type":"ISSN"}]},"item_10001_version_type_20":{"attribute_name":"Author's flag","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_970fb48d4fbd8a85","subitem_version_type":"VoR"}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2022-02-28"}],"displaytype":"detail","filename":"jacs.1c12599(1).pdf","filesize":[{"value":"5.1 MB"}],"format":"application/pdf","license_note":"Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (https://creativecommons.org/licenses/by-nc-nd/4.0/)","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"jacs.1c12599(1)","url":"https://oist.repo.nii.ac.jp/record/2576/files/jacs.1c12599(1).pdf"},"version_id":"928b50ab-8f8f-4867-b93e-271e678b458f"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization","subitem_title_language":"en"}]},"item_type_id":"10001","owner":"30","path":["228"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-02-28"},"publish_date":"2022-02-28","publish_status":"0","recid":"2576","relation_version_is_last":true,"title":["An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization"],"weko_creator_id":"30","weko_shared_id":30},"updated":"2023-06-26T11:23:53.110404+00:00"}