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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Macgregor, Stuart Alan
University of St Andrews
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (6/6 displayed)
- 2021Controlled synthesis of well-defined polyaminoboranes on scale using a robust and efficient catalystcitations
- 2021A series of crystallographically characterized linear and branched σ-alkane complexes of rhodiumcitations
- 2016A Rhodium-Pentane Sigma-Alkane Complexcitations
- 2016Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchangecitations
- 2012Synthesis and characterization of a rhodium(I) σ-alkane complex in the solid statecitations
- 2005The F/Ph rearrangement reaction of [(Ph3P)3RhF], the fluoride congener of Wilkinson's catalystcitations
Places of action
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article
The F/Ph rearrangement reaction of [(Ph3P)3RhF], the fluoride congener of Wilkinson's catalyst
Abstract
<p>The fluoride congener of Wilkinson's catalyst, [(Ph<sub>3</sub>P) <sub>3</sub>RhF] (1), has been synthesized and fully characterized. Unlike Wilkinson's catalyst, 1 easily activates the inert C-Cl bond of ArCl (Ar = Ph, ρ-tolyl) under mild conditions (3 h at 80 °C) to produce trans-[(Ph <sub>3</sub>P)<sub>2</sub>Rh(Ph<sub>2</sub>PF)(Cl)] (2) and ArPh as a result of C-Cl, Rh-F, and P-C bond cleavage and C-C, Rh-Cl, and P-F bond formation. In benzene (2-3 h at 80 °C), 1 decomposes to a 1:1 mixture of trans-[(Ph <sub>3</sub>P)<sub>2</sub>Rh(Ph<sub>2</sub>PF)(F)] (3) and the cyclometalated complex [(Ph<sub>3</sub>P)<sub>2</sub>Rh(Ph<sub>2</sub>PC<sub>6</sub>H <sub>4</sub>)] (4). Both the chloroarene activation and the thermal decomposition reactions have been shown to occur via the facile and reversible F/Ph rearrangement reaction of 1 to cis-[(Ph<sub>3</sub>P)<sub>2</sub>Rh(Ph) (Ph<sub>2</sub>PF)] (5), which has been isolated and fully characterized. Kinetic studies of the F/Ph rearrangement, an intramolecular process not influenced by extra phosphine, have led to the determination of E<sub>a</sub> = 22.7 ± 1.2 kcal mol<sup>-1</sup>, ΔH‡ 22.0 ± 1.2 kcal mol<sup>-1</sup>, and ΔS‡ = -10.0 ± 3.7 eu. Theoretical studies of F/Ph exchange with the [(PH<sub>3</sub>)<sub>2</sub>(PH <sub>2</sub>Ph)RhF] model system pointed to two possible mechanisms: (i) Ph transfer to Rh followed by F transfer to P (formally oxidative addition followed by reductive elimination, pathway 1) and (ii) F transfer to produce a metallophosphorane with subsequent Ph transfer to Rh (pathway 2). Although pathway 1 cannot be ruled out completely, the metallophosphorane mechanism finds more support from both our own and previously reported observations. Possible involvement of metallophosphorane intermediates in various P-F, P-O, and P-C bond-forming reactions at a metal center is discussed.</p>