Krämer, Tobias, Gyton, Matthew R., Bustos, I., Sinclair, M. J. G., Tan, Sze-yin, Wedge, C. J., Macgregor, S. A. and Chaplin, Adrian B. (2023) 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. Journal of the American Chemical Society, 145 (25). pp. 14087-14100. doi:10.1021/jacs.3c04167 ISSN 0002-7863.
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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).
| Item Type: | Journal Article |
|---|---|
| Alternative Title: | |
| Subjects: | Q Science > QD Chemistry |
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry |
| Library of Congress Subject Headings (LCSH): | Free radicals (Chemistry), Palladium compounds, Platinum compounds, Organometallic compounds |
| Journal or Publication Title: | Journal of the American Chemical Society |
| Publisher: | American Chemical Society |
| ISSN: | 0002-7863 |
| Official Date: | 28 June 2023 |
| Dates: | Date Event 28 June 2023 Published 15 June 2023 Available 22 May 2023 Accepted |
| Volume: | 145 |
| Number: | 25 |
| Page Range: | pp. 14087-14100 |
| DOI: | 10.1021/jacs.3c04167 |
| Status: | Peer Reviewed |
| Publication Status: | Published |
| Access rights to Published version: | Open Access (Creative Commons open licence) |
| Date of first compliant deposit: | 24 May 2023 |
| Date of first compliant Open Access: | 28 June 2023 |
| RIOXX Funder/Project Grant: | Project/Grant ID RIOXX Funder Name Funder ID EP/K035681/1 [EPSRC] Engineering and Physical Sciences Research Council |
| Related URLs: | |
| URI: | https://wrap.warwick.ac.uk/175992/ |
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