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Chemistry ; 20(23): 6991-7000, 2014 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-24753131


The synthesis, structure, and solution-state behavior of clothespin-shaped binuclear trans-bis(ß-iminoaryloxy)palladium(II) complexes doubly linked with pentamethylene spacers are described. Achiral syn and racemic anti isomers of complexes 1-3 were prepared by treating Pd(OAc)2 with the corresponding N,N'-bis(ß-hydroxyarylmethylene)-1,5-pentanediamine and then subjecting the mixture to chromatographic separation. Optically pure (100 % ee) complexes, (+)-anti-1, (+)-anti-2, and (+)-anti-3, were obtained from the racemic mixture by employing a preparative HPLC system with a chiral column. The trans coordination and clothespin-shaped structures with syn and anti conformations of these complexes have been unequivocally established by X-ray diffraction studies. (1)H NMR analysis showed that (±)-anti-1, (±)-anti-2, syn-2, and (±)-anti-3 display a flapping motion by consecutive stacking association/dissociation between cofacial coordination planes in [D8]toluene, whereas syn-1 and syn-3 are static under the same conditions. The activation parameters for the flapping motion (ΔH(≠) and ΔS(≠)) were determined from variable-temperature NMR analyses as 50.4 kJ mol(-1) and 60.1 J mol(-1) K(-1) for (±)-anti-1, 31.0 kJ mol(-1) and -22.7 J mol(-1) K(-1) for (±)-anti-2, 29.6 kJ mol(-1) and -57.7 J mol(-1) K(-1) for syn-2, and 35.0 kJ mol(-1) and 0.5 J mol(-1) K(-1) for (±)-anti-3, respectively. The molecular structure and kinetic parameters demonstrate that all of the anti complexes flap with a twisting motion in [D8]toluene, although (±)-anti-1 bearing dilated Z-shaped blades moves more dynamically than I-shaped (±)-anti-2 or the smaller (±)-anti-3. Highly symmetrical syn-2 displays a much more static flapping motion, that is, in a see-saw-like manner. In CDCl3, (±)-anti-1 exhibits an extraordinary upfield shift of the (1)H NMR signals with increasing concentration, whereas solutions of (+)-anti-1 and the other syn/anti analogues 2 and 3 exhibit negligible or slight changes in the chemical shifts under the same conditions, which indicates that anti-1 undergoes a specific heterochiral association in the solution state. Equilibrium constants for the dimerizations of (±)- and (+)-anti-1 in CDCl3 at 293 K were estimated by curve-fitting analysis of the (1)H NMR chemical shift dependences on concentration as 26 M(-1) [KD(racemic)] and 3.2 M(-1) [KD(homo)], respectively. The heterochiral association constant [KD(hetero)] was estimated as 98 M(-1), based on the relationship KD(racemic) = 1/2 KD(homo) +1/4 KD(hetero). An inward stacking motif of interpenetrative dimer association is postulated as the mechanistic rationale for this rare case of heterochiral association.