A series of lower rim-functionalised calix[4]arenes bearing 1,3-positioned phosphorus(III) ligands L1111–L999 have been synthesized and their coordinative properties examined. L1111 and L222
{5,11,17,23-tetra-tert-butyl-25,27-bis[2-(diphenylphosphino)ethoxy]- and -25,27-bis(diphenylphosphinomethoxy)-26,28-bis(3-oxabutyloxy)calix[4]arene} react with [Rh(nbd)(THF)2]BF4 (nbd = 1,5-norbornadiene; THF = tetrahydrofuran) to afford in high yield the complexes [Rh(nbd)L1111]BF4 and [Rh(nbd)L222]BF4, respectively, where the calixarene behaves as a P,P′ chelator. Both complexes catalyse hydroformylation of styrene at comparable rates, the linear∶branched aldehyde ratio being 5∶95. The presence of the ether side groups did not exert a noticeable effect on the selectivity nor the catalytic activity. Reaction of L1111–L888 with [Pd(η3-C3H4Me)(THF)2]BF4 gave the corresponding cationic chelate complexes [Pd(η3-C3H4Me)Liii]BF4 that are active in the catalytic alkylation of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate. Owing to the presence of a non-planar Pd–allyl fragment, the achiral calixarene subunits of some of these complexes are no longer C2v-symmetrical, as evidenced by the 1H and 13C NMR spectra that show non-equivalent side groups. Selective chelation via the two phosphorus atoms was also observed in the complexes [RuCl(p-MeC6H4Pri)Liii]BF4 (Liii = L333 or L444) obtained by reaction of the amide phosphines Liii with [RuCl(p-MeC6H4Pri)(THF)2]BF4 [L333 = 5,11,17,23-tetra-tert-butyl-25,27-bis(diethylcarbamoylmethoxy)-26,28-bis(diphenylphosphinomethoxy)- and L444 = 5,11,17,23-tetra-tert-butyl-25,27-bis(diphenylphosphinomethoxy)-26,28-bis{(1-(R)-phenylethyl)carbamoylmethoxy}-calix[4]arene]. Reaction of L333 or L444 with neutral [RuCl2(p-MeC6H4Pri)]2 afforded the bimetallic complexes [{RuCl(p-MeC6H4Pri)}2Liii] where the calixarene acts as a P,P′ bridging ligand. Reaction of AgBF4 with calix-crown L999
{25,27-bis(diethoxyphosphinoxy)-26,28-(3,6,9-trioxaundecane-1,11-dioxy)calix[4]arene} resulted in quantitative formation of the complex [AgL999]BF4 in which the silver(I) ion lies inside the cavity constituted by the crown ether fragment and the two phosphorus arms. As revealed by a single crystal X-ray diffraction study, the Ag+ ion has a trigonal P2O coordination environment with a P–Ag–P angle of 134.74(4)°.