Self‐assembled highly positively charged allyl‐Pd crowns: cavity‐pocket driven interactions of fluoroanions
A series of dodecanuclear highly positively charged homo‐ and heterometallamacrocycles [{Pd(η 3 ‐2‐Me‐C 3 H 4 )} 6 (4‐PPh 2 py) 12 {M 2 (tpbz)} 3 ] 18+ (M = Pd, Pt; tpbz = 1,2,4,5‐tetrakis(diphenylphosphanylbenzene) were synthesized by the quantitative self‐assembly of {Pd(η 3 ‐2‐Me‐C 3 H 4 )} + , {...
| Authors: | , , , , , , |
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| Format: | article |
| Status: | Versión aceptada para publicación |
| Publication Date: | 2020 |
| Country: | España |
| Institution: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repository: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2445/162865 |
| Online Access: | https://hdl.handle.net/2445/162865 |
| Access Level: | Open access |
| Keyword: | Lligands Ions metàl·lics Química supramolecular Ligands Metal ions Supramolecular chemistry |
| Summary: | A series of dodecanuclear highly positively charged homo‐ and heterometallamacrocycles [{Pd(η 3 ‐2‐Me‐C 3 H 4 )} 6 (4‐PPh 2 py) 12 {M 2 (tpbz)} 3 ] 18+ (M = Pd, Pt; tpbz = 1,2,4,5‐tetrakis(diphenylphosphanylbenzene) were synthesized by the quantitative self‐assembly of {Pd(η 3 ‐2‐Me‐C 3 H 4 )} + , {M 2 (tpbz)} 4+ and 4‐PPh 2 py moieties in 2:1:4 molar ratio. The cationic assemblies were obtained as salts of different fluorinated anions that display diverse sizes and electronic properties, namely BF 4 ‐ , PF 6 ‐ , SbF 6 ‐ and CF 3 SO 3 ‐ . The new crown‐like metallamacrocycles showed remarkable differences in their NMR spectra due to the presence of the different counteranions. On the basis of the observed variations, the metallacycles have been tested as catalytic precursors in allylic alkylation reactions. The anion‐dependent activity and selectivity has been analysed and compared with that of the corresponding monometallic allylic corners [Pd(η 3 ‐2‐Me‐C 3 H 4 )(4‐PPh 2 py) 2 ]X (X = BF 4 ‐ , PF 6 ‐ , SbF 6 ‐ , CF 3 SO 3 ‐ ). DFT calculations have been employed in order to help to the interpretation of the experimental data and to model the anion‐crown interactions. |
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