{"@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/1360004233251912960.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1021/om301147n"}},{"identifier":{"@type":"URI","@value":"https://pubs.acs.org/doi/pdf/10.1021/om301147n"}}],"resourceType":"学術雑誌論文(journal article)","dc:title":[{"@value":"Polymerization of Phenylacetylenes Using Rhodium Catalysts Coordinated by Norbornadiene Linked to a Phosphino or Amino Group"}],"description":[{"notation":[{"@value":"The novel rhodium (Rh) catalysts [{nbd-(CH2)4-X}RhR] (1, X = PPh2, R = Cl; 2, X = NPh2, R = Cl; 3, X = PPh2, R = triphenylvinyl; nbd = 2,5-norbornadiene) were synthesized, and their catalytic activities were examined for the polymerization of phenylacetylene (PA) and its derivatives. Rh-103 NMR spectroscopy together with DFT calculations (B3LYP/6-31G*-LANL2DZ) indicated that catalyst 1 exists in a mononuclear 16-electron state, while 2 exists in dinuclear states. Catalyst 1 converted PA less than 1% in the absence of triethylamine (Et3N). Addition of Et3N and extension of the polymerization time enhanced the monomer conversion. On the other hand, catalysts 2 and 3 quantitatively converted PA in the absence of Et3N to afford the polymer in good yields. Catalyst 3 achieved two-stage polymerization of PA."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1420845751152235264","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"50768223"},{"@type":"NRID","@value":"1000050768223"},{"@type":"NRID","@value":"9000018460583"},{"@type":"NRID","@value":"9000256896389"},{"@type":"NRID","@value":"9000257732082"},{"@type":"NRID","@value":"9000409313783"},{"@type":"RESEARCHMAP","@value":"https://researchmap.jp/111aaa"}],"foaf:name":[{"@value":"Naoya Onishi"}],"jpcoar:affiliationName":[{"@value":"Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura Campus, Nishikyo-ku, Kyoto 615-8510, 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membranes"}]}],"relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360002216635711872","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Helical Polyacetylene: Asymmetric Polymerization in a Chiral Liquid-Crystal Field"}]},{"@id":"https://cir.nii.ac.jp/crid/1360004230263108736","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Molecular weight dependence of helical conformation of amino acid‐based polyphenylacetylenes"}]},{"@id":"https://cir.nii.ac.jp/crid/1360004233630043264","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Synthesis of block copolymers using end-functionalized polyacetylenes as macroinitiators"}]},{"@id":"https://cir.nii.ac.jp/crid/1360011145127390976","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Acetylenic 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Synthesis, Characterization, Redox Properties, and Solid-State Structure of the Octahedral Clusters [Fe<sub>5</sub>RhN(CO)<sub>15</sub>]<sup>2</sup><sup>-</sup>, [Fe<sub>5</sub>IrN(CO)<sub>15</sub>]<sup>2</sup><sup>-</sup>, and [Fe<sub>4</sub>Rh<sub>2</sub>N(CO)<sub>15</sub>]<sup>-</sup>. Infrared and Nuclear Magnetic Resonance Spectroscopic Studies on the Interstitial Nitride"}]},{"@id":"https://cir.nii.ac.jp/crid/1360574095819490176","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"Transition Metal NMR Spectroscopy. One‐bond\n            <sup>103</sup>\n            Rh,\n            <sup>15</sup>\n            N coupling constants of axial and equatorial ligands in rhodoximes"}]},{"@id":"https://cir.nii.ac.jp/crid/1360574096111189376","@type":"Article","relationType":["references"],"jpcoar:relatedTitle":[{"@value":"<i>Ab initio</i> effective core potentials for molecular calculations. 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