{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1050001202647193216.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"HDL","@value":"http://hdl.handle.net/2241/117562"}},{"identifier":{"@type":"URI","@value":"https://tsukuba.repo.nii.ac.jp/records/27639"}},{"identifier":{"@type":"DOI","@value":"10.1039/c0dt01283a"}},{"identifier":{"@type":"URI","@value":"http://pubs.rsc.org/en/content/articlepdf/2011/DT/C0DT01283A"}},{"identifier":{"@type":"PMID","@value":"21431146"}}],"resourceType":"学術雑誌論文(journal article)","dc:title":[{"@language":"en","@value":"Deprotonation/protonation of coordinated secondary thioamide units of pincer ruthenium complexes: Modulation of voltammetric and spectroscopic characterization of the pincer complexes"}],"dc:language":"en","description":[{"notation":[{"@value":"New pincer ruthenium complexes, [Ru(SCS)(tpy)]PF(6) (1) (SCS = 2,6-bis(benzylaminothiocarbonyl)phenyl), tpy = 2,2':6',2''-terpyridyl) and [Ru(SNS)(tpy)]PF(6) (2) (SNS = 2,5-bis(benzylaminothiocarbonyl)pyrrolyl), having κ(3)SCS and κ(3)SNS pincer ligands with two secondary thioamide units were synthesized by the reactions of [RuCl(3)(tpy)] with N,N'-dibenzyl-1,3-benzenedicarbothioamide (L1) and N,N'-dibenzyl-2,5-1H-pyrroledicarbothioamide (L2), respectively, and their chemical and electrochemical properties were elucidated. The structure of 1 was determined by X-ray crystallography. The complexes 1 and 2 showed a two-step deprotonation reaction by treatment with 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), and the addition of DBU led to a shift of the metal-centered redox couples to a lower potential by 720 and 550 mV, respectively. The di-deprotonated complexes were also studied by (1)H-NMR and UV-vis spectroscopy. The addition of methanesulfonic acid (MSA) to the di-deprotonated complexes enabled the recovery of 1 and 2, indicating that the thioamide moiety underwent a reversible deprotonation-protonation process, which resulted in regulating the redox potentials of the metal center. The Pourbaix diagram of 1 revealed that 1 underwent a one-proton/one-electron transfer process in the pH range of 5.83-10.35, and a two-proton/one-electron process at a pH of over 10.35, indicating that the deprotonation/protonation process of the complexes is related to proton-coupled electron transfer (PCET)."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1070302459071518465","@type":"Researcher","foaf:name":[{"@language":"en","@value":"Teratani Takuya"}]},{"@id":"https://cir.nii.ac.jp/crid/1420001326233711232","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"60322674"},{"@type":"NRID","@value":"1000060322674"},{"@type":"NRID","@value":"9000413530078"},{"@type":"NRID","@value":"9000016812432"},{"@type":"NRID","@value":"9000021111092"},{"@type":"NRID","@value":"9000016653424"},{"@type":"NRID","@value":"9000256015569"},{"@type":"NRID","@value":"9000413530911"},{"@type":"NRID","@value":"9000413527702"},{"@type":"NRID","@value":"9000255702886"},{"@type":"NRID","@value":"9000256028647"},{"@type":"NRID","@value":"9000017675162"},{"@type":"NRID","@value":"9000257733705"},{"@type":"NRID","@value":"9000330328661"},{"@type":"NRID","@value":"9000256025214"},{"@type":"NRID","@value":"9000413489765"},{"@type":"NRID","@value":"9000255700860"},{"@type":"NRID","@value":"9000413489258"},{"@type":"NRID","@value":"9000257707981"},{"@type":"NRID","@value":"9000001376914"},{"@type":"NRID","@value":"9000002002019"},{"@type":"NRID","@value":"9000001732351"},{"@type":"NRID","@value":"9000258597371"},{"@type":"NRID","@value":"9000413527570"},{"@type":"RESEARCHMAP","@value":"https://researchmap.jp/read0080494"}],"foaf:name":[{"@language":"en","@value":"Koizumi Take-aki"}]},{"@id":"https://cir.nii.ac.jp/crid/1070302459071518466","@type":"Researcher","foaf:name":[{"@language":"en","@value":"Yamamoto Takakazu"}]},{"@id":"https://cir.nii.ac.jp/crid/1030003658400473856","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"00029274"},{"@type":"NRID","@value":"1000000029274"}],"foaf:name":[{"@language":"en","@value":"Tanaka Koji"}]},{"@id":"https://cir.nii.ac.jp/crid/1420845751155838464","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"90204809"},{"@type":"NRID","@value":"1000090204809"},{"@type":"ORCID","@value":"0000-0002-6034-1582"},{"@type":"NRID","@value":"9000018232917"},{"@type":"NRID","@value":"9000413532110"},{"@type":"NRID","@value":"9000413530076"},{"@type":"NRID","@value":"9000321422370"},{"@type":"NRID","@value":"9000257897781"},{"@type":"NRID","@value":"9000272989631"},{"@type":"NRID","@value":"9000010553243"},{"@type":"NRID","@value":"9000413530910"},{"@type":"NRID","@value":"9000345264490"},{"@type":"NRID","@value":"9000021111095"},{"@type":"NRID","@value":"9000399497804"},{"@type":"NRID","@value":"9000257750028"},{"@type":"NRID","@value":"9000413535408"},{"@type":"NRID","@value":"9000283148340"},{"@type":"NRID","@value":"9000257702506"},{"@type":"NRID","@value":"9000257731849"},{"@type":"NRID","@value":"9000413492203"},{"@type":"NRID","@value":"9000413492174"},{"@type":"NRID","@value":"9000398144471"},{"@type":"NRID","@value":"9000257899039"},{"@type":"NRID","@value":"9000257734407"},{"@type":"NRID","@value":"9000413489256"},{"@type":"NRID","@value":"9000257732254"},{"@type":"NRID","@value":"9000259336189"},{"@type":"NRID","@value":"9000413492149"},{"@type":"NRID","@value":"9000310331325"},{"@type":"NRID","@value":"9000283393886"},{"@type":"NRID","@value":"9000413515633"},{"@type":"NRID","@value":"9000413527568"},{"@type":"NRID","@value":"9000345260927"},{"@type":"NRID","@value":"9000257720396"},{"@type":"NRID","@value":"9000244892969"},{"@type":"RESEARCHMAP","@value":"https://researchmap.jp/read0069298"}],"foaf:name":[{"@language":"en","@value":"KANBARA Takaki"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"14779226"},{"@type":"EISSN","@value":"14779234"},{"@type":"NCID","@value":"AA11810256"}],"prism:publicationName":[{"@language":"en","@value":"Dalton Transactions"}],"dc:publisher":[{"@value":"The Royal Society of Chemistry"}],"prism:publicationDate":"2011-09","prism:volume":"40","prism:number":"35","prism:startingPage":"8879","prism:endingPage":"8886"},"reviewed":"false","dcterms:accessRights":"http://purl.org/coar/access_right/c_abf2","dc:rights":["© The Royal Society of Chemistry 2011"],"url":[{"@id":"https://tsukuba.repo.nii.ac.jp/records/27639"},{"@id":"http://pubs.rsc.org/en/content/articlepdf/2011/DT/C0DT01283A"}],"project":[{"@id":"https://cir.nii.ac.jp/crid/1040282257002006272","@type":"Project","projectIdentifier":[{"@type":"KAKEN","@value":"20002005"},{"@type":"JGN","@value":"JP20002005"},{"@type":"URI","@value":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20002005/"}],"notation":[{"@language":"ja","@value":"金属錯体触媒による電気エネルギーと化学エネルギーの相互変換反応の開発"},{"@language":"en","@value":"Metal Catalyzed Reversible Conversion between Chemical Energy and Electrical One"}]}],"relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050001202617548672","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["references"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Nickel(II) complexes bearing a pincer ligand containing thioamide units: Comparison between SNS- and SCS-pincer 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