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dc.contributor.authorCaputo, Christine
dc.contributor.authorJennings, Michael
dc.contributor.authorTuononen, Heikki
dc.contributor.authorJones, Nathan
dc.date.accessioned2015-11-24T12:09:36Z
dc.date.available2015-11-24T12:09:36Z
dc.date.issued2009
dc.identifier.citationCaputo, C., Jennings, M., Tuononen, H., & Jones, N. (2009). Phospha-Fischer Carbenes: Synthesis, Structure, Bonding, and Reactions of Pd(0)− and Pt(0)−Phosphenium Complexes. <i>Organometallics</i>, <i>28</i>(4), 990-1000. <a href="https://doi.org/10.1021/om800973v" target="_blank">https://doi.org/10.1021/om800973v</a>
dc.identifier.otherCONVID_19243798
dc.identifier.otherTUTKAID_38379
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47802
dc.description.abstractThe analogy between cationic group 10 metal−phosphenium complexes and Fischer carbenes has been formalized through structural and reactivity studies and by energy decomposition analysis (EDA) of the M−P bond. The studied compounds were the three-coordinate, 16-electron species [(NHPMes)M(PPh3)2]OTf (M = Pt (1) and Pd (2); [NHPMes]+ is the N-heterocyclic phosphenium (NHP) cation, [tiebar above startPN(2,4,6-Me3-C6H2)CH2CH2tiebar above endN(2,4,6-Me3-C6H2)]+, OTf = trifluoromethanesulfonate); these were made by reaction of [NHPMes]OTf with M(PPh3)4. The metal−phosphenium bond in both compounds was dominated by metal-to-ligand π-donation. This differed from the M−C bonds in the analogous N-heterocyclic carbene (NHC) complexes, (NHCMes)M(PPh3)2 (M = Pt (6), Pd (7)), which were instead predominantly σ-type. Structural determination of 1 by X-ray crystallography revealed the shortest yet reported Pt−P bond of 2.107(3) Å, consistent with significant double-bond character, and trigonal planar geometries at both the P-atom within the [NHPMes]+ ligand (∑(angles) = 359.99°) and at the Pt-atom (∑(angles) = 360.00°), which indicated that 1 was better described as a Pt(0)−phosphenium rather than as a Pt(II)−phosphide. Reactions of 1 and 2 with excess PMe3 cleanly gave the four-coordinate species [(NHPMes)M(PMe3)3]OTf (M = Pt (3) and Pd (4)), while reaction of 1 with bis(diphenylphosphino)ethane (dppe) gave [(NHPMes)Pt(dppe-κ2P)(dppe-κP)]OTf (5). Hydrolysis of these complexes resulted in metal hydrides and oxidation of the NHP to phosphine oxide via intial nucleophilic attack of water at the P-atom in the coordinated [NHPMes]+ ligand, which was calculated to bear a significantly positive charge in 1.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesOrganometallics
dc.subject.otherfosfa-Fischer karbeenit
dc.subject.othermetallikompleksit
dc.subject.otherPhospha-Fischer carbenes
dc.subject.othermetal complexes
dc.titlePhospha-Fischer Carbenes: Synthesis, Structure, Bonding, and Reactions of Pd(0)− and Pt(0)−Phosphenium Complexes
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511203741
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2015-11-20T10:15:06Z
dc.type.coarjournal article
dc.description.reviewstatuspeerReviewed
dc.format.pagerange990-1000
dc.relation.issn0276-7333
dc.relation.numberinseries4
dc.relation.volume28
dc.type.versionacceptedVersion
dc.rights.copyright© 2009 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.relation.doi10.1021/om800973v


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