Silver(I) and copper(I) complexes supported by fully fluorinated 1,3,5-triazapentadienyl ligands.

Synthesis of the perfluorinated 1,3,5-triazapentadiene [N{(CF(3))C(C(6)F(5))N}(2)]H and the use of its conjugate base as a supporting ligand for the isolation of silver(i) and copper(i) complexes are reported. Some of the related chemistry involving [N{(C(3)F(7))C(C(6)F(5))N}(2)](-) (that has bulkier -C(3)F(7) groups on the 1,3,5-triazapentadienyl ligand backbone) is also presented. X-ray crystallographic data show a wide variety of structures ranging from intermolecular, hydrogen-bonded chain structure for [N{(CF(3))C(C(6)F(5))N}(2)]H with a twisted W-shaped N(3)C(2) core, monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Ag(CN(t)Bu)(2) and [N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag(CN(t)Bu)(2) where the κ(1)-bonded triazapentadienyl ligand bonding to the metal fragment via the central nitrogen atom, monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Ag(PPh(3))(2) and [N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag(PPh(3))(2) that feature κ(1)-bonded triazapentadienyl ligand bonding to the metal fragment via one of the terminal nitrogen atoms, to that of the monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Cu(CN(t)Bu)(2) containing a κ(2)-bonded triazapentadienyl ligand and a U-shaped NCNCN ligand backbone.

Assessment of the electronic structure of 2,2'-pyridylpyrrolides as ligands.

The ligand class 2,2'-pyridylpyrrolide is surveyed, both for its structural features and its electronic structure, when attached to monovalent K, Cu, Ag, Au, and Rh. The influence of pyrrolide ring substituents is studied, as well as the question of push/pull interaction between the pyridyl and pyrrolide halves. The π donor ability of the pyrrolide is found to be less than that of an analogous phenyl.

Synthesis and characterization of silver(I) adducts supported solely by 1,3,5-triazapentadienyl ligands or by triazapentadienyl and other N-donors.

Halogenated 1,3,5-triazapentadienyl ligands [N{(C(3)F(7))C(C(6)F(5))N}(2)](-), [N{(CF(3))C(C(6)F(5))N}(2)](-) and [N{(C(3)F(7))C(2,6-Cl(2)C(6)H(3))N}(2)](-), alone or in combination with other N-donors like CH(3)CN, CH(3)(CH(2))(2)CN, and N(C(2)H(5))(3), have been used in the stabilization of thermally stable, two-, three- or four-coordinate silver(i) adducts. X-Ray crystallographic analyses of {[N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag}(n), {[N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag(NCCH(3))}(n), {[N{(C(3)F(7))C(2,6-Cl(2)C(6)H(3))N}(2)]Ag(NCCH(3))}(n), {[N{(CF(3))C(C(6)F(5))N}(2)]Ag(NCCH(3))(2)}(n) and {[N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag(NCC(3)H(7))}(n) revealed the presence of bridging 1,3,5-triazapentadienyl ligands bonded to silver through terminal nitrogen atoms. These adducts are polymeric in the solid state.

Comparing the tuberculin skin test and T-SPOT.TB blood test in children.

Background: Interferon-γ-release assays (IGRAs) have been developed for the diagnosis of tuberculosis infection, but few data are available for children. There currently is no reference standard for the diagnosis of tuberculosis infection.

Objective: To compare the performance of 1 IGRA, the T-SPOT.

Ligand influence on metal aggregation: a unique bonding mode for pyridylpyrrolides.

The synthesis and characterization of a Cu(I) complex with a cis-bidentate monoanionic nitrogenous ligand, 2-pyridylpyrrolide, L, is reported. This shows binding of one base B = MeCN or CO per copper in a species LCu(B), but this readily releases the volatile ligand under vacuum with aggregation of transient LCu to a mixture of two enantiomers of a chiral trimer: a zwitterion containing inequivalent Cu(I) centers, possible via a new bonding mode of pyridylpyrrolide, and one with nitrogen lone pairs donating to two different metals. Density functional theory calculations show the energetics of both ligand binding and aggregation (including dimer and monomer alternatives), as well as the ability of this ligand to rotate away from planarity to accommodate a bridging structural role.

Synthesis and catalytic activity of an electron-deficient copper-ethylene triazapentadienyl complex.

The copper(i) ethylene complex [N{(C(3)F(7))C(Dipp)N}(2)]Cu(C(2)H(4)) (Dipp = 2,6-diisopropylphenyl) has been synthesized by treating [N{(C(3)F(7))C(Dipp)N}(2)]Cu(NCCH(3)) with ethylene at room temperature. [N{(C(3)F(7))C(Dipp)N}(2)]Cu(C(2)H(4)) is an air stable, yellow solid. X-Ray crystallographic data of [N{(C(3)F(7))C(Dipp)N}(2)]Cu(C(2)H(4)) show that the 1,3,5-triazapentadienyl ligand coordinates to copper in kappa(2)-fashion.

Monomeric copper(I), silver(I), and gold(I) alkyne complexes and the coinage metal family group trends.

A series of thermally stable, easily isolable, monomeric, and isoleptic coinage metal alkyne complexes have been reported. Treatment of [N{(C(3)F(7))C(Dipp)N}(2)]Li (the lithium salt of the 1,3,5-triazapentadiene [N{(C(3)F(7))C(Dipp)N}(2)]H) with AuCl, CF(3)SO(3)Ag or CF(3)SO(3)Cu in the presence of 3-hexyne led to the corresponding coinage metal alkyne complex [N{(C(3)F(7))C(Dipp)N}(2)]M(EtC[triple bond]CEt) in good yield (M = Au, Ag, Cu; Dipp = 2,6-diisopropylphenyl). X-ray crystal structures of the three coinage metal alkynes are remarkably similar, and show the presence of trigonal-planar metal sites with eta(2)-bonded 3-hexyne.

Gold(I) ethylene and copper(I) ethylene complexes supported by a polyhalogenated triazapentadienyl ligand.

A rare gold(I) ethylene complex and the closely related copper(I) ethylene adduct have been isolated using [N{(C3F7)C(2,6-Cl2C6H3)N}2]- as the supporting ligand. [N{(C3F7)C(2,6-Cl2C6H3)N}2]Au(C2H4) (1) is an air-stable solid. It features a U-shaped triazapentadienyl ligand backbone and a three-coordinate, trigonal-planar gold center.

Thermally stable gold(I) beta-diketiminate complexes.

The synthesis and X-ray structures of gold(I) adducts supported by beta-diketiminates have been reported. {[HC{(H)C(2,4,6-Br(3)C(6)H(2))N}(2)]Au}(2) and {[HC{(H)C(Dipp)N}(2)]Au}(2) [Dipp = 2,6-(i-Pr)(2)C(6)H(3)] are easily isolable solids and feature 12-membered macrocyclic ring structures. beta-Diketiminate ligands adopt a W-shaped conformation.

Syntheses of highly fluorinated 1,3,5-triazapentadienyl ligands and their use in the isolation of copper(I)-carbonyl and copper(I)-ethylene complexes.

Fully fluorinated triazapentadienyl ligand [N{(C3F7)C(C6F5)N}2]- and the related [N{(C3F7)C(2-F,6-(CF3)C6H3)N}2]- have been synthesized in good yield via a convenient route and used in the isolation of three- and four-coordinate copper(I)-carbon monoxide complexes. They show fairly high nu(CO) values (>2100 cm(-1)), indicating the presence of electron-poor Cu sites. The copper(I)-ethylene adduct [N{(C3F7)C(C6F5)N}2]Cu(C2H4), featuring a three-coordinate Cu site, has also been synthesized using [N{(C3F7)C(C6F5)N}2]CuNCCH3 and C2H4.