Seven E[Cu(OR)2] copper(I) complexes (E = K(+), {K(18C6)}(+) (18C6 = [18]crown-6), or Ph4P(+); R = C4F9, CPhMe(F)2, and CMeMe(F)2) have been prepared and their reactivity with O2 studied. The K[Cu(OR)2] species react with O2 in a copper-concentration-dependent manner such that 2:1 and 3:1 Cu/O2 adducts are observed manometrically at -78 °C. Analogous reactivity with O2 is not observed with the {K(18C6)}(+) or Ph4P(+) derivatives. Solution conductivity data demonstrate that these K[Cu(OR)2] complexes do not behave as 1:1 electrolytes in solution. The K(+) ions induce aggregation of multiple [Cu(OR)2](-) units through K⋅⋅⋅F/O interactions and thereby effect irreversible O2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K(+) ions. Intramolecular hydroxylation of ligand aryl and alkyl C-H bonds is observed. Nucleophilic reactivity with CO2 is observed for the oxygenated Cu complexes and a Cu(II) carbonate has been isolated and characterized.

Homoleptic fluorinated alkoxide complexes have been prepared from KOC4F9, 1, via salt metathesis routes. One four-coordinate K{K(18C6)}[Co(OC4F9)4], 2, and four three-coordinate complexes: {K(18C6)}[Fe(OC4F9)3], 3, {K(18C6)}[Co(OC4F9)3], 4, {K(18C6)}[Cu(OC4F9)3], 5, and {K(18C6)}[Zn(OC4F9)3], 6, have been prepared and all except 5 have been characterized crystallographically. Compounds 3, 4, and 6 are very rare examples of monomeric, trigonal alkoxide complexes. All compounds have been characterized with UV-vis and IR spectroscopy, solution magnetic susceptibility, and elemental analysis. In solution, compound 2 exists in an equilibrium with 4 and 1, which has been probed with cyclic voltammetry, supporting energetically different Co2+/Co3+ potentials in the three-coordinate (E(p,a) = approximately 1.2 V vs Fc/Fc+) and four-coordinate (E(p,a) = approximately 0.9 V) geometries. The ligand field engendered by the perfluoro-t-butoxide ligand has been studied with DFT calculations on 4 and the hypothetical [Co(OC4H9)3]- as well as the previously reported [Co(mes)3]- and [Co{N(TMS)2}3]- showing significant -type interactions in the xy plane as well as above and below for the two alkoxide species.

Seven new homoleptic complexes of the form A2[M(pin(F))2] have been synthesized with the dodecafluoropinacolate (pin(F))(2-) ligand, namely (Me4N)2[Fe(pin(F))2], 1; (Me4N)2[Co(pin(F))2], 2; ((n)Bu4N)2[Co(pin(F))2], 3; {K(DME)2}2[Ni(pin(F))2], 4; (Me4N)2[Ni(pin(F))2], 5; {K(DME)2}2[Cu(pin(F))2], 7; and (Me4N)2[Cu(pin(F))2], 8. In addition, the previously reported complexes K2[Cu(pin(F))2], 6, and K2[Zn(pin(F))2], 9, are characterized in much greater detail in this work. These nine compounds have been characterized by UV-vis spectroscopy, cyclic voltammetry, elemental analysis, and for paramagnetic compounds, Evans method magnetic susceptibility. Single-crystal X-ray crystallographic data were obtained for all complexes except 5. The crystallographic data show a square-planar geometry about the metal center in all Fe (1), Ni (4), and Cu (6, 7, 8) complexes independent of countercation. The Co species exhibit square-planar (3) or distorted square-planar geometries (2), and the Zn species (9) is tetrahedral. No evidence for solvent binding to any Cu or Zn complex was observed. Solvent binding in Ni can be tuned by the countercation, whereas in Co only strongly donating Lewis solvents bind independent of the countercation. Indirect evidence (diffuse reflectance spectra and conductivity data) suggest that 5 is not a square-planar compound, unlike 4 or the literature K2[Ni(pin(F))2]. Cyclic voltammetry studies reveal reversible redox couples for Ni(III)/Ni(II) in 5 and for Cu(III)/Cu(II) in 8 but quasi-reversible couples for the Fe(III)/Fe(II) couple in 1 and the Co(III)/Co(II) couple in 2. Perfluorination of the pinacolate ligand results in an increase in the central C-C bond length due to steric clashes between CF3 groups, relative to perhydropinacolate complexes. Both types of pinacolate complexes exhibit O-C-C-O torsion angles around 40°. Together, these data demonstrate that perfluorination of the pinacolate ligand makes possible highly unusual and coordinatively unsaturated high-spin metal centers with ready thermodynamic access to rare oxidation states such as Ni(III) and Cu(III).

The paramagnetic trigonal-planar copper complexes {K(18C6)}-[Cu II (OC(CH 3 )(CF 3 ) 2 ) 3 ] (2) and K[Cu II (OC(C 6 H 5 )(CF 3 ) 2 ) 3 ] (3) have been prepared and characterized, including X-ray crystallography, in 61% and 3% yields, respectively. The latter complex does not form preferentially, because CuBr 2 and KOC(C 6 H 5 )(CF 3 ) 2 ) 3 also form the diamagnetic complexes {K(18C6)}-[K 2 {Cu I (OC(C 6 H 5 )(CF 3 ) 2 ) 2 } 3 ] (4) and {K(18C6)}[Cu III (OC(C 6 H 4 )(CF 3 ) 2 ) 2 ] (5). These species were characterized by X-ray crystallography, UV−vis spectroscopy, 1 H, 13 C{ 1 H}, and 19 F{ 1 H} NMR spectroscopy, and elemental analysis. The unique organocuprate Cu(III) species with {O 2 C 2 } coordination was formed by ortho metalation of two phenyl rings, resulting in trans-{O 2 C 2 } coordination of Cu(III), and is stable at room temperature in the solid state and in dark solutions of THF.

Although the application of silver nanoparticles to commercial antibacterial items is well-established, there have been increasing concerns that such particles might leach out, particularly into laundry water from textile products. A recently developed process wherein silver nanoparticles are synthesized in situ within the cotton fiber itself promises, however, to achieve the desired washing durability. In this study, the silver release behavior of the silver nanoparticle-infused cotton fabric during consecutive launderings in water and a detergent solution was analyzed. Silver nanoparticles (12 ± 3 nm in diameter) were uniformly produced throughout the entire volume of cotton fiber with a concentration of 3017 ± 56 mg/kg. A combination of colorimetric, spectroscopic, and elemental analyses showed (1) nonlinear silver release behavior, with a rapid release from externally formed nanoparticles during the initial washing and a plateau-like release from internally formed nanoparticles during extended washing, and (2) superior nanoparticle-leach resistance compared to those in commercial and laboratory-prepared textiles analyzed in the literature. The internal nanoparticles immobilized within cotton fiber exhibited persistent antibacterial activity after 50 home laundering cycles.