A novel hemilabile calix[4],quinoline-based P,N-ligand: Coordination chemistry and complex characterisation

The synthesis of the calix[4]arene-based P,N-ligand 3 (5,11,17,23-tetra-tert-butyl-25-[(2-quinolylmethyl)oxy]-26,27,28-(mu(3)-phosphorustrioxy)calix[4]arene), in which the nitrogen atom-containing moiety has been introduced at the lower rim of the cavity prior to P-functionalisation, is described and its coordination properties investigated. In the crystal structure, the calix[4]-cavity adopts a cone conformation with an exo orientation of the phosphorus lone pair enabling P-N chelation. H-1, C-13, P-31 and H-1{N-15} HMQC NMR spectra indicated that, in complexes [PdCl(CH3)(3)] (4) and [Rh(CO)Cl(3)] (5), ligand 3 coordinates in a chelating fashion, while in cis-[PtCl2(3)(2)] (6) and [Rh(acac)(CO)(3)] (7) it behaves as a monodentate ligand, coordinating via the phosphorus atom only. X-Ray crystal structure determinations were performed for [PdCl(CH3)(3)] (4) and cis-[PtCl2(3)(2)] (6). The cationic Pd complex [Pd(CH3)(CH3CN)(3)][PF6] (8) was found to be active in a CO/ethylene copolymerisation reaction. Good selectivities were observed for the Pd-catalysed allylic alkylation of cinnamyl acetate with in situ prepared catalysts. [Rh(acac)(CO)(2)] modified with ligand 3 catalyses the hydroformylation of 1-octene with low selectivities towards linear aldehydes. High-pressure NMR experiments on the hydrido carbonyl rhodium( 3) were inconclusive, different species were formed.