Silver coordination chemistry of a new versatile "Janus"-type N(2),O(2)-bichelating donor, formation of an unprecedented supramolecular network of binuclear silver building blocks containing a five-coordinate beta-diketonate, and isolation of unexpected silver-tin-silver heterotrimetallic complexes from silver metathesis reactions.

Synthetic, spectroscopic, and single-crystal X-ray studies are reported for several complexes of silver(I) with the N(2),O(2)-bichelating Q(py) ligand (HQ(py) = 1-(2-pyridyl)-3-methyl-4-trifluoroacetylpyrazol-5-one). Direct interaction between HQ(py) and AgNO(3) in methanol, in the presence of NaOCH(3), affords derivative Ag(Q(py)), showing a polynuclear structure composed of dinuclear building blocks with two different Ag environments and two Q(py) donors differently connected. By adding neutral ligands such as PR(3) (R = Ph, Cy, C(6)H(4)-o-CH(3), C(6)H(4)-p-F, Bu(i)) to Ag(Q(py)), dinuclear Ag(Q(py))(PR(3)) derivatives have been isolated, containing bridging N(2),O-exotridentate Q(py) donors spanning a pair of AgPR(3) moieties. Reaction of Ag(Q(py))(PPh(3)) with excess PPh(3) produces the mononuclear Ag(Q(py))(PPh(3))(2) containing N(2)-chelate Q(py). Ag(Q(py)) interacts with 1,2-bis(diphenylphosphino)ethane (dppe) yielding the derivative Ag(Q(py))(dppe), having a polynuclear structure in the solid state which is seemingly disrupted in solution, with the formation of two new species, a mononuclear neutral compound and a dinuclear ionic one. By the interaction of Ag(Q(py)) with nitrogen donors L (L = imidazole (imH), 1-methylimidazole (Meim), 1-methyl-2-mercaptoimidazole (Hmimt), 1,10-phenanthroline (phen)), mononuclear species Ag(Q(py))(L) have been obtained, where Q(py) is coordinated to silver in N(2)-chelating mode. Ag(Q(py))(PPh(3))(2) reacts with SnRCl(3) (R = Ph, Bu(n)) affording heterotrimetallic [[(Ph(3)P)(2)AgCl](2)SnRCl(3)] derivatives.

Crystal structures and vibrational and solution and solid-state (CPMAS) NMR spectroscopic studies in triphenyl phosphine, arsine, and stibine silver(I) bromate systems, (R3E)xAgBrO3 (E = P, As, Sb; x = 1-4).

Adducts of triphenyl phosphine, triphenyl arsine, and triphenyl stibine with silver(I) bromate have been synthesized and characterized both in solution ((1)H and ESI MS spectroscopy) and in the solid state (IR, single-crystal X-ray structure analysis). The triphenyl phosphine complexes have been also investigated by (31)P[(1)H] solution and (31)P cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy. The topology of the structures in the solid state was found to depend on the nature of EPh(3) and on the stoichiometric ratio AgBrO(3)/EPh(3). In AgBrO(3)/PPh(3) (1:1)(4) (1) and AgBrO(3)/PPh(3) (1:2) (2), the bromate is in the unfamiliar and hitherto structurally uncharacterized role of coordinating ligand, the complex having a mononuclear form in 2 and a less familiar tetrameric form in 1. In AgBrO(3)/AsPh(3) (1:4).CH(3)OH (7) and AgBrO(3)/SbPh(3) (1:4).C(2)H(5)OH (11), the cations are the familiar homoleptic [Ag(EPh(3))(4)](+) array with the bromate role simply that of counterion. The AgBrO(3)/AsPh(3) (1:2)(2).0.7"H(2)O" derivative (6) is binuclear L(2)Ag(mu-BrO(3))(2)AgL(2) with a four-membered ring core (L = AsPh(3)).