calixarenes and phosphine

We investigate the synthesis of accessible calix[4]arene-bound gold clusters consisting of open "coordinatively unsaturated" active sites, using a comparative approach that relies on calix[4]arene ligands with various upper- and lower-rim substituents. In contrast with a reported Au(I)-tert-butyl-calixarene phosphine complex, which exhibits a single cone conformer in solution, the H upper-rim analog exhibits multiple conformers in solution. This contrasts with observations of the tert-butyl upper-rim analog, which exhibits a single cone conformer in solution under similar conditions. In the solid state, as determined by single-crystal X-ray diffraction, both H and tert-butyl upper-rim analogs exhibit exclusively cone conformer. A detailed structural analysis of these two solid-state structures highlights a CH-π interaction involving a methoxy lower-rim substituent and phenyl substituent on P as the key feature that enforces a tight configuration of Au(I) atoms on the same side of the calix[4]arene lower-rim plane. We hypothesize that such a configuration promotes chelation of the ligand to a gold surface and facilitates the synthesis of small Au11-sized clusters after reduction of both complexes. The new cluster, like the one reported with the tert-butyl analog, has an extraordinary 25% of surface atoms that are open and accessible to a 2-NT (2-naphthalenethiol) probe in solution. We also investigated the effect of calix[4]arene lower-rim substituents that coordinate to the metal, by using N-heterocyclic carbene (NHC) functional groups rather than phosphines. Four small (<1.6 nm diameter) calix[4]arene NHC-bound gold clusters were synthesized, including three using novel calix[4]arene NHC ligands. The smallest calix[4]arene NHC-bound Au cluster consisted of a 1.2 nm gold core, and its number density of accessible and open surface sites was measured. This required development of a new titration method for open sites on gold clusters, using a SAMSA fluorescein dye molecule, which excites and emits at lower energy relative to the previously used 2-NT probe. The number density of open sites on the new calix[4]arene NHC-bound gold cluster measured by the SAMSA fluorescein probe strongly supports the generality of a mechanical model of accessibility, which does not depend on the functional group involved in binding to the gold surface and rather depends on the relative radii of curvature of bound ligands and the gold cluster core.

Topics: Calixarenes; Gold; Heterocyclic Compounds; Ligands; Methane; Models, Molecular; Molecular Structure; Organogold Compounds; Phenols; Phosphines

Self-assembly and characterization of novel heterodimeric diphosphine capsules formed by multiple ionic interactions and composed of one tetracationic diphosphine ligand and one complementary tetraanionic calix[4]arene are described. Encapsulation of a palladium atom within a diphosphine capsule is achieved successfully by using the metal complex of the tetracationic diphosphine ligand for the assembly process. In this templated approach to metal encapsulation, the transition-metal complex is an integrated part of the capsule with the transition metal located inside the capsule and is not involved in the assembly process. We present two approaches for capsule assembly by mixing solutions of the precharged building blocks in methanol and mixing solutions of the neutral building blocks in methanol. The scope of the diphosphine capsules and the metallodiphosphine capsules is easily extended by applying tetracationic diphosphine ligands with different backbones (ethylene, diphenyl ether, and xanthene) and cationic binding motifs (p-C(6)H(4)-CH(2)-ammonium, m-C(6)H(4)-ammonium, and m-C(6)H(4)-guanidinium). These tetracationic building blocks with different flexibilities and shapes readily associate into capsules with the proper capsular structure, as is indicated by (1)H NMR spectroscopy, 1D NOESY, ESI-MS, and modeling studies.

Topics: Calixarenes; Capsules; Catalysis; Coordination Complexes; Palladium; Phenols; Phosphines; Transition Elements

Self-assembly and characterization of heterodimeric diphosphine capsules formed by multiple ionic interactions are described. The first type of capsules is composed of one novel tetrasulfonato-xantphos ligand and one complementary tetraammonium calix[4]arene. Encapsulation of a transition metal is achieved by self-assembly of a rhodium complex containing the tetraanionic diphosphine ligand and a tetracationic calix[4]arene. The second type of capsules is composed of two oppositely charged diphosphine ligands: one tetrasulfonato-xantphos and one tetraammonium-diphosphine (of the xantphos-, DPEphos-, and 1,2-bis(diphenylphosphino)ethane (dppe)-type). Bis(metallo) capsules, that is, simultaneous encapsulation of two different transition metals, are created by self-assembly of a palladium or platinum complex containing a tetracationic ligand and a rhodium complex containing a tetraanionic ligand. Diphosphine ligands with different flexibilities and shapes assemble into metallocapsules with a proper capsular structure, as is indicated by (1)H NMR and 1D-NOESY spectroscopy, ESIMS, and modeling studies.

Topics: Calixarenes; Capsules; Ligands; Palladium; Phenols; Phosphines; Platinum; Rhodium; Transition Elements

Topics: Butanols; Calixarenes; Catalysis; Gold; Metal Nanoparticles; Metals; Naphthalenes; Phosphines; Sulfhydryl Compounds

The potential of molecules that combine the properties of a conical cavity with those of a covalently-linked transition-metal centre is highlighted through the assessment of cyclodextrin- and calixarene-derived podands ("cavitand" ligands) in coordination chemistry and catalysis. Metallocavitands with coordination sites directed towards the interior of the generic cavity provide interesting systems for studying host-guest complexation processes, their enhanced strength of metal-ion binding allowing for regioselective catalysis in a confined environment, and stabilisation of coordination complexes of unusual forms. Where cavitands have exo-oriented podand arms, the intrinsic dynamics of the cavity can dramatically modify metal chelation behaviour and the catalytic properties of the complexes. Such functionalised cavities are also useful as metal-ion transporters.

Topics: Calixarenes; Chelating Agents; Chlorides; Crystallography, X-Ray; Cyclodextrins; Ethylenes; Ligands; Metals; Models, Molecular; Molecular Conformation; Phosphines