Ion Pairing and Allyl Dynamics in a Series of [Pd(η3-allyl)(N,Nchelate)]( anion) Salts. On the Influence of the BPh4 - Anion
Articolo
Data di Pubblicazione:
2009
Citazione:
Ion Pairing and Allyl Dynamics in a Series of [Pd(η3-allyl)(N,Nchelate)](
anion) Salts. On the Influence of the BPh4
- Anion / A. Moreno, P.S. Pregosin, B. Fuentes, L.F. Veiros, A. Albinati, S. Rizzato. - In: ORGANOMETALLICS. - ISSN 0276-7333. - 28:22(2009), pp. 6489-6506. [10.1021/om900697e]
Abstract:
Aseries of BPh4
- and other Pd-allyl salts of the form [Pd(η3-allyl)(N,N-chelate)](anion) (η3-allyl=
CH2C(Me)CH2, 3, and PhCHCHCHPh, 4) have been prepared and studied via PGSE diffusion and
other forms of NMR spectroscopy together with X-ray and DFT calculations. The diffusion data
reveal that the BPh4
- salts show a very substantial amount of ion pairing in CD2Cl2 solution. Both
the solution Overhauser studies and the X-ray results are consistent with a BPh4
- position that brings
one or more phenyl groups very close to the N,N-chelate, and this would facilitate phenylation
reactions. Variable-temperature and magnetization transfer NMR measurements reveal allyl and
ligand dynamics that fall under the general heading of “apparent rotation”.DFTcalculations suggest
that this isomerization process in 3 and 4 is solvent assisted and proceeds with Pd-Nbond breaking.
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
A. Moreno, P.S. Pregosin, B. Fuentes, L.F. Veiros, A. Albinati, S. Rizzato
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