Abstract:
Transition metal complexes derived from anionic polyimido ligands are very limited in the literature. Here we describe the deprotonation of alkyl substituted phosphoric triamides with bis(benzonitrile)palladium dichloride which results in the formation of chloro‐bridged hexanuclear palladium(II) clusters of formula {Pd3[(NR)3PO](Cl)3}2 in octahedral and prismatic geometries. These clusters consist of two trinuclear Pd3‐motifs, each cis‐protected by a tris(alkylimido)phosphate trianion, which are linked together by six μ2‐Cl bridges. A staggered arrangement of the two imido‐Pd3 units results in the formation of octahedral clusters (R=iBu, nBu, cHex, iPr and nPr), while an eclipsed conformation (R=tBu) gives rise to a prismatic cluster. A similar prismatic configuration was obtained for the mixed‐bridged clusters {Pd3[(NR)3PO](OAc)2(Cl)}2 (R=cHex and iPr), formed in the reaction involving the corresponding phosphoric triamide, Pd(OAc)2 and Pd(PhCN)2Cl2. The reaction of an octahedral cluster {Pd3[(NnPr)3PO](Cl)3}2 with 1,1’‐ferrocene dicarboxylic acid (FDC−H) gave the prismatic cluster {Pd3[(NnPr)3PO](FDC)(Cl)}2 which again consists of a mixed‐bridged environment with FDC and Cl− linkers. Further, treatment of the octahedral {Pd3[(NnPr)3PO](Cl)3}2 cluster with iPrNH2, a stronger nucleophile, leads to its symmetric cleavage and forms the trinuclear cluster {Pd3[(NR)3PO]Cl3(R'NH2)3}. We have also shown the catalytic activity of some of these Pd(II) complexes in the Suzuki reactions in both organic and aqueous phase conditions which suggest that all these imido‐Pd(II) clusters are still suitable for catalytic reactions.