Reaction of [Pd(1-3-η-allyl)Cl]2 with lithium triazenide (triazenide = p-XC6H4NN-NC6H4X-p; X = Cl, H, CH3) affords dimeric complexes of the type [Pd(1-3-η-allyl)(triazenide)]2. In the solid state the triazenido ligands are bridging two palladium atoms with their terminal nitrogen atoms, as shown by a preliminary X-ray determination of the complex with X = CH3. The allyl groups are stereochemically equivalent. 1H NMR spectra demonstrate the presence of two conformers in solution. The major component has the same configuration found in the solid. The other conformer has stereochemically non equivalent allyl groups. The concentration ratio of the two conformers is independent of the temperature, suggesting the absence of intramolecular processes and of palladium- triazenido bond breaking. This point is discussed also by comparing the (1-3-η-allyl)(triazenide)palladium (II) dimers with the closely related(1-3-η-allyl)(acetate)palladium(II) complexes. © 1975.
Allylic palladium(II) triazenido complexes: synthesis and spectroscopic studies
TONIOLO, Luigi;
1975-01-01
Abstract
Reaction of [Pd(1-3-η-allyl)Cl]2 with lithium triazenide (triazenide = p-XC6H4NN-NC6H4X-p; X = Cl, H, CH3) affords dimeric complexes of the type [Pd(1-3-η-allyl)(triazenide)]2. In the solid state the triazenido ligands are bridging two palladium atoms with their terminal nitrogen atoms, as shown by a preliminary X-ray determination of the complex with X = CH3. The allyl groups are stereochemically equivalent. 1H NMR spectra demonstrate the presence of two conformers in solution. The major component has the same configuration found in the solid. The other conformer has stereochemically non equivalent allyl groups. The concentration ratio of the two conformers is independent of the temperature, suggesting the absence of intramolecular processes and of palladium- triazenido bond breaking. This point is discussed also by comparing the (1-3-η-allyl)(triazenide)palladium (II) dimers with the closely related(1-3-η-allyl)(acetate)palladium(II) complexes. © 1975.I documenti in ARCA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.