Abstract
AbstractAcetatopalladium(II) complexes of four different 1,3‐bis(2‐arylimino)isoindoline ligands (bai's) with different degrees of steric congestion have been prepared and were characterized by NMR and XRD with respect to nuclearity and coordination mode. In particular, the propensity for heteroaryl ring rotation and C–H activation has been investigated. Palladium(II) ions bind to bai ligands in different coordination modes, either as classical Werner‐type N,N,N bonded complexes or―after pyridyl ring rotation and C–H activation―as carbometalated C,N,N chelates. In the latter case two (bai*)Pd(OAc) subunits have been found to dimerize via two bridging Pd(OAc) moieties in the solid and in solution. These stable and electroneutral tetranuclear species are of low solubility in non‐donor solvents, but break up into soluble dinuclear species of unknown composition upon the addition of DMSO, azide or cyanide. Attempts to activate C–C bonds by this strategy were not successful. Surprisingly, the exchange of the terminal pyridines by pyrimidines does not result in the formation of oligonuclear or oligomeric species. Besides the degree of steric hindrance, three more factors, solubility of the products, stoichiometry of metal precursor and charge compensation, have been identified to govern the outcome of the metalation of these bai ligands.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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