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- Title
Self‐Assembled, Highly Positively Charged, Allyl–Pd Crowns: Cavity‐Pocket‐Driven Interactions of Fluoroanions.
- Authors
Ferrer, Montserrat; Gallen, Albert; Gutiérrez, Albert; Martínez, Manuel; Ruiz, Eliseo; Lorenz, Yvonne; Engeser, Marianne
- Abstract
A series of dodecanuclear highly positively charged homo‐ and heterometallamacrocycles [{Pd(η3‐2‐Me‐C3H4)}6(4‐PPh2py)12{M2(tpbz)}3]18+ (M=Pd, Pt; tpbz=1,2,4,5‐tetrakis(diphenylphosphanyl)benzene were synthesized by the quantitative self‐assembly of {Pd(η3‐2‐Me‐C3H4)}+, {M2(tpbz)}4+ and 4‐PPh2py moieties in 2:1:4 molar ratio. The cationic assemblies were obtained as salts of different fluorinated anions with diverse sizes and electronic properties, namely BF4−, PF6−, SbF6− and CF3SO3−. 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(η3‐2‐Me‐C3H4)(4‐PPh2py)2]X (X=BF4−, PF6−, SbF6−, CF3SO3−). DFT calculations have been employed in order to help to the interpretation of the experimental data and to model the anion–crown interactions.
- Subjects
ALLYLIC alkylation; METALLACYCLES; ALLYL compounds; CROWNS; DATA modeling
- Publication
Chemistry - A European Journal, 2020, Vol 26, Issue 35, p7847
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202000316