Diffusion NMR investigations were carried out in CD(2)Cl(2) for a series of neutral (1-7) and cationic (8-10) square planar palladium complexes. Diffusion data were elaborated through a modified Stokes-Einstein equation that takes into account the size and shape of molecules. The hydrodynamic volume at infinite dilution of all complexes was found to be similar to the crystallographic volume and always much larger than the van der Waals volume. The self-aggregation tendency of [Pd(N,C )(N,N)][PF(6)] ionic complexes [(N,C) = (C(6)H(4)-(Ph)C(O)-C=N-Et); 8, (N,N) = 2,2'-bipirydine; 9, (N,N) = (2,6-(iPr)(2)-C(6)H(3))N=C(Me)-C(Me)=N(2,6-(iPr)(2)-C(6)H(3)); 10, (N,N) = (2,6-(iPr)(2)-C(6)H(3))N=C(R')-C(R')=N(2,6-(iPr)(2)-C(6)H(3)), R(2)' = naphthalene-1,8-diyl] was investigated by performing (1)H and (19)F diffusion experiments as a function of the concentration. Clear evidence for the formation of ion triples containing two cationic units was obtained for 8, most likely due to the establishment of a weak Pd center dot center dot center dot O interaction. The tendency to form ion triples was much reduced in 9 and 10, having an increased steric hindrance in the apical positions. While 9 showed the usual tendency to afford a mixture of free ions and ion pairs, solvated ions were the predominant species in the case of 10 even at high concentration values (approaching 100 mM). (C) 2009 Elsevier B. V. All rights reserved.
Diffusion NMR studies on neutral and cationic square planar palladium(II) complexes
ZUCCACCIA, Daniele
2010-01-01
Abstract
Diffusion NMR investigations were carried out in CD(2)Cl(2) for a series of neutral (1-7) and cationic (8-10) square planar palladium complexes. Diffusion data were elaborated through a modified Stokes-Einstein equation that takes into account the size and shape of molecules. The hydrodynamic volume at infinite dilution of all complexes was found to be similar to the crystallographic volume and always much larger than the van der Waals volume. The self-aggregation tendency of [Pd(N,C )(N,N)][PF(6)] ionic complexes [(N,C) = (C(6)H(4)-(Ph)C(O)-C=N-Et); 8, (N,N) = 2,2'-bipirydine; 9, (N,N) = (2,6-(iPr)(2)-C(6)H(3))N=C(Me)-C(Me)=N(2,6-(iPr)(2)-C(6)H(3)); 10, (N,N) = (2,6-(iPr)(2)-C(6)H(3))N=C(R')-C(R')=N(2,6-(iPr)(2)-C(6)H(3)), R(2)' = naphthalene-1,8-diyl] was investigated by performing (1)H and (19)F diffusion experiments as a function of the concentration. Clear evidence for the formation of ion triples containing two cationic units was obtained for 8, most likely due to the establishment of a weak Pd center dot center dot center dot O interaction. The tendency to form ion triples was much reduced in 9 and 10, having an increased steric hindrance in the apical positions. While 9 showed the usual tendency to afford a mixture of free ions and ion pairs, solvated ions were the predominant species in the case of 10 even at high concentration values (approaching 100 mM). (C) 2009 Elsevier B. V. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
