dc.contributor.author | Krämer, Tobias | |
dc.contributor.author | Bustos Rosas, Itxaso | |
dc.contributor.author | Sinclair, Matthew J. G. | |
dc.contributor.author | Gyton, Matthew R. | |
dc.contributor.author | Tan, Sze-yin | |
dc.contributor.author | Wedge, Christopher J. | |
dc.contributor.author | Macgregor, Stuart A. | |
dc.contributor.author | Chaplin, Adrian B. | |
dc.date.accessioned | 2024-01-29T13:43:52Z | |
dc.date.available | 2024-01-29T13:43:52Z | |
dc.date.issued | 2023-06-15 | |
dc.identifier.citation | Journal of the American Chemical Society 145(25) : 14087-14100 (2023) | es_ES |
dc.identifier.issn | 1520-5126 | |
dc.identifier.uri | http://hdl.handle.net/10810/64415 | |
dc.description.abstract | One-electron oxidation of palladium(0) and platinum(0) bis(phosphine) complexes enables isolation of a homologous series of linear d9 metalloradicals of the form [M(PR3)2]+ (M = Pd, Pt; R = tBu, Ad), which are stable in 1,2-difluorobenzene (DFB) solution for >1 day at room temperature when partnered with the weakly coordinating [BArF4]− (ArF = 3,5-(CF3)2C6H3) counterion. The metalloradicals exhibit reduced stability in THF, decreasing in the order palladium(I) > platinum(I) and PAd3 > PtBu3, especially in the case of [Pt(PtBu3)2]+, which is converted into a 1:1 mixture of the platinum(II) complexes [Pt(PtBu2CMe2CH2)(PtBu3)]+ and [Pt(PtBu3)2H]+ upon dissolution at room temperature. Cyclometalation of [Pt(PtBu3)2]+ can also be induced by reaction with the 2,4,6-tri-tert-butylphenoxyl radical in DFB, and a common radical rebound mechanism involving carbon-to-metal H-atom transfer and formation of an intermediate platinum(III) hydride complex, [Pt(PtBu2CMe2CH2)H(PtBu3)]+, has been substantiated by computational analysis. Radical C–H bond oxidative addition is correlated with the resulting MII–H bond dissociation energy (M = Pt > Pd), and reactions of the metalloradicals with 9,10-dihydroanthracene in DFB at room temperature provide experimental evidence for the proposed C–H bond activation manifold in the case of platinum, although conversion into platinum(II) hydride derivatives is considerably faster for [Pt(PtBu3)2]+ (t1/2 = 1.2 h) than [Pt(PAd3)2]+ (t1/2 ∼ 40 days). | es_ES |
dc.description.sponsorship | We thank the EPSRC (EP/K035681/1, T.K., S.A.M.; DTP studentship to M.J.G.S.), European Research Council (ERC grant agreement 637313, M.R.G., A.B.C.), Spanish Ministry of Universities and European Union (Margarita Salas grant funded by the European Union-NextGenerationEU, I.B.), and Royal Society (UF100592, UF150675, A.B.C.) for financial support. T.K. and S.A.M. acknowledge the DJEI/DES/SFI/HEA Irish Centre for High-End Computing (ICHEC) and ARCHER2 UK National Supercomputing Facility for the provision of high-performance computing facilities and support. EPR facilities were provided by the Spectroscopy RTP at the University of Warwick. High-resolution mass-spectrometry data were collected using instruments purchased through support from Advantage West Midlands and the European Regional Development Fund. Crystallographic data were collected using an instrument that received funding from the ERC under the European Union’s Horizon 2020 research and innovation program (grant agreement No. 637313). T.K. thanks Dr. Ragnar Bjornsson (CEA Grenoble) for insightful discussions. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | ACS | es_ES |
dc.relation | info:eu-repo/grantAgreement/EC/H2020/637313 | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | * |
dc.subject | anions | es_ES |
dc.subject | Palladium | es_ES |
dc.subject | Platinum | es_ES |
dc.subject | reactivity | es_ES |
dc.subject | stability | es_ES |
dc.title | Stability and C–H Bond Activation Reactions of Palladium(I) and Platinum(I) Metalloradicals: Carbon-to-Metal H-Atom Transfer and an Organometallic Radical Rebound Mechanism | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | © 2023 The Authors. Published by American Chemical Society. This publication is licensed under
CC-BY 4.0. | es_ES |
dc.relation.publisherversion | https://pubs.acs.org/doi/10.1021/jacs.3c04167 | es_ES |
dc.identifier.doi | 10.1021/jacs.3c04167 | |
dc.contributor.funder | European Commission | |
dc.departamentoes | Química aplicada | es_ES |
dc.departamentoeu | Kimika aplikatua | es_ES |