{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,6]],"date-time":"2025-11-06T06:22:19Z","timestamp":1762410139711,"version":"build-2065373602"},"reference-count":33,"publisher":"MDPI AG","issue":"5","license":[{"start":{"date-parts":[[2023,3,2]],"date-time":"2023-03-02T00:00:00Z","timestamp":1677715200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100010801","name":"Xunta de Galicia","doi-asserted-by":"publisher","award":["GRC2019\/14"],"award-info":[{"award-number":["GRC2019\/14"]}],"id":[{"id":"10.13039\/501100010801","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Treatment of the double nuclear complex 1a, di-\u03bc-cloro-bis[N-(4-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph2PCH2CH2)2PPh (triphos) and NH4PF6 gave the single nuclear species 2a, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate). Reaction of 2a with Ph2PCH2CH2NH2 in refluxing chloroform via a condensation reaction of the amine and formyl groups to produce the C=N double bond, gave 3a, 1-N-(cyclohexylamine)-4- N-(diphenylphosphinoethylamine)palladium(triphos)(hexafluorophasphate); a potentially bidentate [N,P] metaloligand. However, attempts to coordinate a second metal by treatment of 3a with [PdCl2(PhCN)2] were to no avail. Notwithstanding, complexes 2a and 3a left to stand in solution spontaneously self-transformed to give in either case the double nuclear complex 10, 1,4-N,N-terephthalylidene(cyclohexilamine)-3,6-[bispalladium(triphos)]di(hexafluorophosphate), after undergoing further metalation of the phenyl ring, then bearing two mutually trans [Pd(Ph2PCH2CH2)2PPh)-P,P,P] moieties: an unprecedented and serendipitous result indeed. On the other hand, reaction of the double nuclear complex 1b, di-\u03bc-cloro-bis[N-(3-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph2PCH2CH2)2PPh (triphos) and NH4PF6 gave the single nuclear species 2b, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate), Treatment of 2b with H2O\/glacial MeCOOH gave cleavage of the C=N double bond and of the Pd\u00b7\u00b7\u00b7N interaction, yielding 5b, isophthalaldehyde-6-palladium(triphos)hexafluorophosphate, which then reacted with Ph2P(CH2)3NH2 to yield complex 6b, N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)di(hexafluorophosphate), with two pairs of non-coordinated nitrogen and phosphorus donor atoms. Treatment of 6b with [PdCl2(PhCN)2], [PtCl2(PhCN)2], or [PtMe2(COD)] gave the new double nuclear complexes 7b, 8b and 9b, palladiumdichloro-, platinumdichloro- and platinumdimethyl[N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)(hexafluorophosphate)-P,P], respectively, showing the behavior of 6b as a palladated bidentate [P,P] metaloligand. The complexes were fully characterized by microanalysis, IR, 1H, and 31P NMR spectroscopies, as appropriate. The X-ray single-crystal analyses for compounds 10 and 5b have been previously described as the perchlorate salts by JM Vila et al.<\/jats:p>","DOI":"10.3390\/molecules28052328","type":"journal-article","created":{"date-parts":[[2023,3,3]],"date-time":"2023-03-03T01:43:00Z","timestamp":1677807780000},"page":"2328","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes"],"prefix":"10.3390","volume":"28","author":[{"given":"Basma","family":"al Janabi","sequence":"first","affiliation":[{"name":"Department of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8536-3382","authenticated-orcid":false,"given":"Francisco","family":"Reigosa","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gemma","family":"Alberdi","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9930-5717","authenticated-orcid":false,"given":"Juan M.","family":"Ortigueira","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jos\u00e9 M.","family":"Vila","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,3,2]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"576","DOI":"10.1021\/cr900279a","article-title":"Cyclometalation using d-block transition metals: Fundamental aspects and recent trends","volume":"110","author":"Albrecht","year":"2010","journal-title":"Chem. 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