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Kristin Bowman-James

Publications and source records attributed to Kristin Bowman-James.

16 recordsLinked to original sources
PubMed2006

Amide-based ligands for anion coordination.

Anion recognition is an active area of research in supramolecular chemistry. The rapidly increasing amount of structural data now allows anion coordination chemistry to be formalized in terms of coordination numbers and geometries based on hydrogen-bonding interactions between the host (ligand) and the guest (anion). This Minireview targets just one class of anion receptors, namely, amide-based ligands. The structural data for a series of five anion shapes are compiled according to coordination number, and distinct commonalities are observed within a given anion topology. The results also indicate a number of similarities between the coordination of anions and transition-metal ions.

Journal Article↗
PubMed2006

Thioamide pincer ligands with charge versatility.

This paper reports the synthesis and characterization of three complexes, two palladium and one platinum, with 2,6-bis-thioamido-phenyl and 2,6-bis-thioamido-pyridine ligands. The ligands show internal charge versatility by losing protons from a phenyl CH (I) or from amide NH's (II and III). The complexes were also examined as Heck catalysts, and the palladacycle, I, was found to be more effective compared to the others. The crystal structures of the complexes are also reported.

Crystallization↗
PubMed2005

Anion binding motifs: topicity and charge in amidocryptands.

An expanded amidocryptand with propyl linkages provides multitopic sites for binding anions and water molecules. Upon quaternization of the two bridgehead amines, the molecular shape changes from an inverted Y to that of a bowl, which is filled with water and topped by the anion.

Journal Article↗
PubMed2005

Tritopic (cascade) and ditopic complexes of halides with an azacryptand.

Structural aspects of the binding of halides in the octaaza cryptand (1,4,11,14,17,24,29,36-octa-azapentacyclo[12.12.12.2(6,9).2(19,22).2(31,34)]-tetratetraconta-6(43),7,9(44),19(41),20,22(42),31(39),32,34(40)-nonaene, N(CH2CH2NHCH2-p-xylyl-CH2NHCH2CH2)3N), L1, were examined for fluoride, chloride, and bromide. Crystallographic results for two different fluoride complexes indicated cascade-like coordination, with two fluoride ions inside the tren-based cavity, bridged by a water molecule. In the two different chloride structures, a single chloride and a water molecule occupied the cavity. The bromide structure contained two crystallographically independent cationic cryptands. Unit A consisted of a bromide on one side of the cavity and three disordered water molecules situated between the cryptand arms on the other side. Unit B also had a bromide inside the cavity at one side, but a single molecule of water was centered at the other side of the cavity. Association constants for the three ions, determined by NMR titrations in aqueous solution at pH 5, revealed log Ka=3.15(5), 3.37(3), and 3.34(4) for fluoride, chloride, and bromide, respectively.

Journal Article↗
PubMed2005

Alfred Werner revisited: the coordination chemistry of anions.

A series of macrocyclic receptors were designed to probe the influence of four factors, hydrogen bonding, charge, dimensionality, and topology, on anion binding. Monocyclic and bicyclic polyammonium and polyamide receptors were synthesized from either 2,2'-diaminodiethylamine derivatives (dien) or 2,2',2''-aminoethylamine (tren) building blocks, plus aromatic or heterocyclic spacers. Supramolecular complexes of these hosts with three simple anion topologies were probed: spherical (halides), trigonal planar (nitrate), and tetrahedral (sulfate). Results indicate a number of corollaries with transition-metal coordination chemistry in terms of binding concepts such as the chelate effect and dual valencies, as well as geometries for anion complexes that are strikingly similar to those observed in transition-metal coordination chemistry.

Anions↗
PubMed2004

Encapsulated sulfates: insight to binding propensities.

Two crystal structures of sulfate inclusion complexes in an aza- and amido-cryptand represent the first examples of encapsulated sulfate in synthetic cryptand receptors and indicate penta- and octa-coordination, respectively.

Amides↗
PubMed2004

Ditopic double pincer palladacycle catalyst for C-C coupling.

A ditopic palladacycle with SCS pincer coordination, L(PdCl)(2) (1), was isolated and structurally characterized and represents the first example of a transition metal complex with a polythioamide-based macrocycle. Preliminary studies of 1 in the catalytic coupling of 4-iodotoluene and styrene indicated it to be robust in the presence of oxygen and high temperatures, with high turnover numbers in relatively short times.

Journal Article↗
PubMed2004

Fluoride-facilitated deuterium exchange from DMSO-d6 to polyamide-based cryptands.

Multiple deuterium exchange between DMSO-d6 and amide hydrogens in two hexaamido cryptand fluoride receptors has been verified by 19F and 2H NMR and FAB mass spectral studies. Structural results for one of the complexes indicate a tricapped trigonal prism hydrogen bond coordination geometry around an encapsulated fluoride, with hydrogen bonds from fluoride to six amide and three phenyl hydrogens.

Journal Article↗
PubMed2004

Anion binding with a tripodal amine.

Binding studies of the tren-based amine, L (N,N',N' '-tris(2-benzylaminoethyl)amine), with inorganic anions and two crystal structures, [H(3)L][H(2)PO(4)](3).H(3)PO(4) and [H(3)L][Br](3), are reported. NMR titration results indicate that the ligand binds H(2)PO(4)(-) and HSO(4)(-) more strongly than NO(3)(-) and halides. In the crystal structure of the phosphate complex, the ligand is triprotonated with the three arms pointing outward in a trigonal-planar-like arrangement. Four phosphate species are associated with the receptor, and have been assigned as three H(2)PO(4)(-) counterions located between each of the tren arms, and an additional H(3)PO(4) molecule above the quasi-planar tren. The structure of the bromide complex is slightly different, although again the tren receptor is triprotonated and quasi-planar, but in this case C(2v)-like symmetry is seen with two of the arms pointed in the same direction with a bromide ion in between. The other two bromides lie outside of the tren arms.

Journal Article↗
PubMed2003

A ditopic azacryptate proton cage.

A tosylated azacryptand readily protonates at the bridgehead amines, becoming a potential ditopic anion receptor. The in-in conformation of the amines facilitates encapsulation of two bromide guests and represents the first structural evidence that a proton cage cryptate can bind two anions internally.

Journal Article↗
PubMed2003

New polyamide cryptand for anion binding.

An anion receptor derived from a tren-based amide cryptand with pyridine spacers has been synthesized and characterized. Two crystal structures are reported: the hydrochloride salt and the fluoride complex. The cryptand shows extremely high binding with fluoride ion in DMSO-d6. Both the crystal structure and solution 19F NMR data indicate an encapsulated fluoride ion with very high symmetry.

Journal Article↗
PubMed2003

Elite new anion ligands: polythioamide macrocycles.

Prototypes for a new class of polythioamide-based macrocycles have been synthesized and anion-binding capabilities assessed. Results indicate higher anion binding for H(2)PO(4)(-), HSO(4)(-), and F(-) for monocycles, but somewhat lessened binding capabilities for bicycles compared with amide corollaries.

Journal Article↗
PubMed2003

Anion receptors: a new class of amide/quaternized amine macrocycles and the chelate effect.

A new class of tetraamide macrocyclic receptors for anions with two quaternized amine functionalities exhibited higher affinities for anions compared with the corresponding neutral amides. In two crystal structures of halide complexes of the prototypes with phenyl and pyridine spacers, the anions are held by hydrogen bonding with the amide hydrogens. The pyridine analogues display higher affinities in general than the phenyl systems, a phenomenon which is attributed to the anion version of the chelate effect.

Journal Article↗