{"@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/1362262944159136000.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/anie.201409454"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201409454"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201409454"}}],"dc:title":[{"@value":"Low‐Temperature N<sub>2</sub> Binding to Two‐Coordinate L<sub>2</sub>Fe<sup>0</sup> Enables Reductive Trapping of L<sub>2</sub>FeN<sub>2</sub><sup>−</sup> and NH<sub>3</sub> Generation"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>The two‐coordinate [(CAAC)<jats:sub>2</jats:sub>Fe] complex [CAAC=cyclic (alkyl)(amino)carbene] binds dinitrogen at low temperature (T<−80 °C). The resulting putative three‐coordinate N<jats:sub>2</jats:sub> complex, [(CAAC)<jats:sub>2</jats:sub>Fe(N<jats:sub>2</jats:sub>)], was trapped by one‐electron reduction to its corresponding anion [(CAAC)<jats:sub>2</jats:sub>FeN<jats:sub>2</jats:sub>]<jats:sup>−</jats:sup> at low temperature. This complex was structurally characterized and features an activated dinitrogen unit which can be silylated at the β‐nitrogen atom. The redox‐linked complexes [(CAAC)<jats:sub>2</jats:sub>Fe<jats:sup>I</jats:sup>][BAr<jats:sup>F</jats:sup><jats:sub>4</jats:sub>], [(CAAC)<jats:sub>2</jats:sub>Fe<jats:sup>0</jats:sup>], and [(CAAC)<jats:sub>2</jats:sub>Fe<jats:sup>−I</jats:sup>N<jats:sub>2</jats:sub>]<jats:sup>−</jats:sup> were all found to be active for the reduction of dinitrogen to ammonia upon treatment with KC<jats:sub>8</jats:sub> and HBAr<jats:sup>F</jats:sup><jats:sub>4</jats:sub>⋅2 Et<jats:sub>2</jats:sub>O at −95 °C [up to (3.4±1.0) equivalents of ammonia per Fe center]. The N<jats:sub>2</jats:sub> reduction activity is highly temperature dependent, with significant N<jats:sub>2</jats:sub> reduction to NH<jats:sub>3</jats:sub> only occurring below −78 °C. This reactivity profile tracks with the low temperatures needed for N<jats:sub>2</jats:sub> binding and an otherwise unavailable electron‐transfer step to generate reactive [(CAAC)<jats:sub>2</jats:sub>FeN<jats:sub>2</jats:sub>]<jats:sup>−</jats:sup>.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1382262944159136001","@type":"Researcher","foaf:name":[{"@value":"Gaël Ung"}]},{"@id":"https://cir.nii.ac.jp/crid/1382262944159136000","@type":"Researcher","foaf:name":[{"@value":"Jonas C. Peters"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"14337851"},{"@type":"EISSN","@value":"15213773"}],"prism:publicationName":[{"@value":"Angewandte Chemie International Edition"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2014-11-13","prism:volume":"54","prism:number":"2","prism:startingPage":"532","prism:endingPage":"535"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201409454"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201409454"}],"createdAt":"2014-11-13","modifiedAt":"2023-09-17","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050013244133092480","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Nitrogen reduction by the Fe sites of synthetic [Mo₃S₄Fe] 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