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Mechanistic Insight...
Mechanistic Insights and Synthetic Explorations of the Photoredox-Catalyzed Activation of Halophosphines
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- Arkhypchuk, Anna I. (författare)
- Uppsala universitet,Syntetisk molekylär kemi
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- Tran, Thuan T. (författare)
- Uppsala universitet,Syntetisk molekylär kemi
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- Charaf, Rima (författare)
- Uppsala universitet,Fysikalisk kemi
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- Hammarström, Leif, 1964- (författare)
- Uppsala universitet,Fysikalisk kemi
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- Ott, Sascha (författare)
- Uppsala universitet,Syntetisk molekylär kemi
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(creator_code:org_t)
- American Chemical Society (ACS), 2023
- 2023
- Engelska.
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 62:45, s. 18391-18398
- Relaterad länk:
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https://doi.org/10.1...
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https://uu.diva-port... (primary) (Raw object)
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- The light-driven activation of halophosphines R2PX (R = alkyl- or aryl, X = Cl, Br) by an IrIII-based photocatalyst is described. It is shown that initially formed secondary phosphines R2PH react readily with the remaining R2PX in a parent–child reaction to form diphosphines R2P–PR2. Aryl-containing diphosphines can be further reduced to secondary phosphines RAr2PH under identical photoredox conditions. Dihalophosphines RPX2 are also activated by the photoredox protocol, giving rise to unusual 3-, 4-, and 5-membered cyclophosphines. Transient absorption studies show that the excited state of the Ir photocatalyst is reductively quenched by the DIPEA (N,N-di-iso-propylethylamine) electron donor. Electron transfer to R2PX is however unexpectedly slow and cannot compete with recombination with the oxidized donor DIPEA•+. As DIPEA is not a perfectly reversible donor, a small proportion of the total IrII population escapes recombination, providing the reductant for the observed transformations.
Ämnesord
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
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