{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,14]],"date-time":"2026-05-14T01:15:49Z","timestamp":1778721349572,"version":"3.51.4"},"reference-count":37,"publisher":"Wiley","issue":"33","license":[{"start":{"date-parts":[[2022,7,6]],"date-time":"2022-07-06T00:00:00Z","timestamp":1657065600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/S023828\/1"],"award-info":[{"award-number":["EP\/S023828\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2022,8,15]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The synthesis of heterometallic transition metal complexes featuring bridging cyaphide ions (C\u2261P<jats:sup>\u2212<\/jats:sup>) is reported. These are synthesized from reactions of Au(IDipp)(CP) (IDipp=1,3\u2010bis(2,6\u2010diisopropylphenyl)imidazol\u20102\u2010ylidene) with electron\u2010rich, nucleophilic transition metal reagents, affording Au(IDipp)(\u03bc<jats:sub>2<\/jats:sub>\u2212C\u2261P)Ni(<jats:sup>Me<\/jats:sup>I<jats:sup><jats:italic>i<\/jats:italic><\/jats:sup>Pr)<jats:sub>2<\/jats:sub> (<jats:sup>Me<\/jats:sup>I<jats:sup><jats:italic>i<\/jats:italic><\/jats:sup>Pr=1,3\u2010diisopropyl\u20104,5\u2010dimethylimidazol\u20102\u2010ylidene) and Au(IDipp)(\u03bc<jats:sub>2<\/jats:sub>\u2212C\u2261P)Rh(Cp*)(PMe<jats:sub>3<\/jats:sub>). These studies reveal that, in contrast to the cyanide ion, bimetallic cyaphido complexes strongly favor a \u03b7<jats:sup>1<\/jats:sup>\u2009:\u2009\u03b7<jats:sup>2<\/jats:sup> coordination mode that maximizes the interaction of the second metal (Ni, Rh) with the \u03c0\u2010manifold of the ion (and not the phosphorus atom lone pair). End\u2010on bridging can be effectively unlocked by blocking the \u03c0\u2010manifold, as demonstrated by reaction of Au(IDipp)(\u03bc<jats:sub>2<\/jats:sub>\u2212C\u2261P)Rh(Cp*)(PMe<jats:sub>3<\/jats:sub>) with an electrophilic transition metal reagent, W(CO)<jats:sub>5<\/jats:sub>(THF), which affords the heterotrimetallic compound Au(IDipp)(\u03bc<jats:sub>3<\/jats:sub>\u2212C\u2261P)[Rh(Cp*)(PMe<jats:sub>3<\/jats:sub>)][W(CO)<jats:sub>5<\/jats:sub>].<\/jats:p>","DOI":"10.1002\/anie.202206783","type":"journal-article","created":{"date-parts":[[2022,6,13]],"date-time":"2022-06-13T11:11:41Z","timestamp":1655118701000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Revealing the Role of the Cyaphide Ion as a Bridging Ligand in Heterometallic Complexes"],"prefix":"10.1002","volume":"61","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0851-655X","authenticated-orcid":false,"given":"Eric S.","family":"Yang","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Oxford Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA U.K."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7311-1663","authenticated-orcid":false,"given":"Jose M.","family":"Goicoechea","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Oxford Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA U.K."}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2022,7,6]]},"reference":[{"key":"e_1_2_3_1_1","first-page":"673","volume-title":"Ullmann's Encyclopedia of Industrial Chemistry","author":"Gail E.","year":"2011"},{"key":"e_1_2_3_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/378701a0"},{"key":"e_1_2_3_3_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.271.5245.49"},{"key":"e_1_2_3_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja508094h"},{"key":"e_1_2_3_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201916199"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201916199"},{"key":"e_1_2_3_6_1","first-page":"363","volume-title":"Ullmann's Encyclopedia of Industrial Chemistry","author":"Pollak P.","year":"2000"},{"key":"e_1_2_3_7_1","unstructured":"We are using this notation to aid the reader. The formal nomenclature for the coordination modes described would be: \u03b71\u2009:\u2009\u03b71=\u03bc-cyanido(cyaphido)-(M)\u03baC\u2009:\u2009(M\u2032)\u03baE(where E=N P); \u03b71\u2009:\u2009\u03b72=\u03bc-(M\u2032)\u03b72-cyanido(cyaphido)-(M)\u03baC; \u03b71\u2009:\u2009\u03b72\u2009:\u2009\u03b71=\u03bc3-(M\u2032)\u03b72-cyanido(cyaphido)-(M)\u03baC-(M\u2032\u2032\u03baE) (where E=N P). Assignment of metal priorities is also recommended."},{"key":"e_1_2_3_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00051a050"},{"key":"e_1_2_3_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00018a043"},{"key":"e_1_2_3_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200602499"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200602499"},{"key":"e_1_2_3_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.9b02471"},{"key":"e_1_2_3_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.7b00590"},{"key":"e_1_2_3_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c07370"},{"key":"e_1_2_3_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00099a007"},{"key":"e_1_2_3_15_1","unstructured":"\u00a0"},{"key":"e_1_2_3_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00089a015"},{"key":"e_1_2_3_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/CS9952400319"},{"key":"e_1_2_3_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b09445"},{"key":"e_1_2_3_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c04417"},{"key":"e_1_2_3_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0cc00018c"},{"key":"e_1_2_3_21_1","unstructured":"See Supporting Information for all experimental details. Deposition Numbers2171578 2171579 2171580 and 2171581contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_3_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201207880"},{"key":"e_1_2_3_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201207880"},{"key":"e_1_2_3_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.200500507"},{"key":"e_1_2_3_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202103093"},{"key":"e_1_2_3_25_1","unstructured":"\u00a0"},{"key":"e_1_2_3_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200901472"},{"key":"e_1_2_3_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200401299"},{"key":"e_1_2_3_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202003167"},{"key":"e_1_2_3_29_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(00)91760-2"},{"key":"e_1_2_3_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct300715s"},{"key":"e_1_2_3_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct800047t"},{"key":"e_1_2_3_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct800172j"},{"key":"e_1_2_3_33_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00894-006-0149-4"},{"key":"e_1_2_3_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp075460u"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202206783","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202206783","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202206783","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,21]],"date-time":"2023-08-21T15:06:19Z","timestamp":1692630379000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202206783"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,7,6]]},"references-count":37,"journal-issue":{"issue":"33","published-print":{"date-parts":[[2022,8,15]]}},"alternative-id":["10.1002\/anie.202206783"],"URL":"https:\/\/doi.org\/10.1002\/anie.202206783","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,7,6]]},"assertion":[{"value":"2022-05-09","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2022-07-06","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202206783"}}