H. V. Rasika Dias

Iron-containing nanomaterials: synthesis, properties, and environmental applications

Available data on the iron-containing nanomaterials are reviewed. Main attention is paid to the following themes: synthetic methods, structures, composition and properties of the nano zerovalent iron (NZVI), and polymorphic forms of iron oxides and FeOOH. Synthetic methods summarized here include a series of physico-chemical methods such as microwave heating, electrodeposition, laser ablation, radiolytical techniques, arc discharge, metal-membrane incorporation, pyrolysis, combustion, reverse micelle and co-deposition routes. We have also included a few “greener” methods. Coated, doped, supported with polymers or inert inorganic materials, core–shell nanostructures, in particular those of iron and its oxides with gold, are discussed. Studies of remediation involving iron-containing nanomaterials are discussed and special attention is paid to the processes of remediation of organic contaminants (chlorine-containing pollutants, benzoic and formic acids, dyes) and inorganic cations (Zn(II), Cu(II), Cd(II) and Pb(II)) and anions (nitrates, bromates, arsenates). Water disinfection (against viruses and bacteria), toxicity and risks of iron nanomaterials application are also examined.

Carbene adducts of magnesium and zinc

Abstract The syntheses and characterizations of adducts of dialkylmagnesium and dialkylzinc with nucleophilic carbenes are described. These carbene adducts are available directly from the reaction of the stable nucleophilic carbenes 1,3-dimesitylimidazol-2-ylidene or 1,3-di(1-adamantyl)imidazol-2-ylidene and the dialkylmetal compounds. The X-ray crystal structures of the 1,3-di(1-adamantyl)imidazol-2-ylidene · diethylzinc adduct and 1,3-dimesitylimidazol-2-ylidene · diethylmagnesium are reported. The adamantyl substituted carbene gave a monomeric metal adduct whereas the mesityl substituted carbene shows a structure with bridging alkyl groups.

C−H Insertion Reactions of Nucleophilic Carbenes

Syntheses and characterizations are described for C−H insertion products derived from 1,3-dimesityldihydroimidazol-2-ylidene (1) with acetylene, acetonitrile, methyl phenyl sulfone, and chloroform. In the reaction with acetylene, both acetylenic H-atoms are reactive so that 1 : 1 and 2 : 1 adducts can be obtained. The acetylene and methyl-phenyl-sulfone adducts are structurally characterized by means of single-crystal X-ray structure determinations. The reactions of 1,3,4,5-tetramethylimidazolidin-2-ylidene (8) with chloroform or chlorodifluoromethane are shown to yield 2-(dihaloalkyl)imidazolium salts that arise from a failure of the intermediate 2-protioimidazolium salt to capture the initially formed halocarbanion.

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. The M-C and M-N bond distances vary in the order Cu < Au < Ag. The bending of the C-C[triple bond]C bond angle is largest for the gold, followed by Cu and Ag adducts. The gold adduct also shows the largest decrease in C[triple bond]C stretching frequency in Raman, while the Ag adduct shows the smallest change compared to that of the uncoordinated alkyne. DFT calculations on [N{(CF(3))C(Ph)N}(2)]M(EtC[triple bond]CEt) and the related ClM(EtC[triple bond]CEt) predict that the M-alkyne bond energy varies in the order Ag < Cu < Au. The gold adducts are also predicted to have the longest C[triple bond]C, largest deviation of C-C[triple bond]C bond angle from linearity, and smallest C[triple bond]C stretching frequency, followed by the Cu and Ag adducts. In these triazapentadienyl coinage metal adducts, the sigma-donation from alkyne --> M dominates over the M --> alkyne pi-back-donation.

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. The copper(I) adduct [N{(C3F7)C(2,6-Cl2C6H3)N}2]Cu(C2H4) (2) also has a similar structure. The 13C NMR signal corresponding to the ethylene carbons of 1 appears at about 64 ppm upfield from the free ethylene, while the ethylene carbons of 2 show a relatively smaller (39 ppm) upfield shift. [N{(C3F7)C(2,6-Cl2C6H3)N}2]M(C2H4) (M=Cu, Au) mediate carbene-transfer reactions from ethyl diazoacetate to saturated and unsaturated hydrocarbons.

Synthesis and biological activity of ester- and amide-functionalized imidazolium salts and related water-soluble coinage metal N-heterocyclic carbene complexes.

N-Heterocyclic carbene (NHC) ligand precursors, namely, HIm(A)Cl [1,3-bis(2-ethoxy-2-oxoethyl)-1H-imidazol-3-ium chloride] and HIm(B)Cl {1,3-bis[2-(diethylamino)-2-oxoethyl]-1H-imidazol-3-ium chloride}, functionalized with hydrophilic groups on the imidazole rings have been synthesized and were used in the synthesis of corresponding carbene complexes of silver(I) and copper(I), {[Im(A)]AgCl}, {[Im(A)]CuCl}, and {[Im(B)](2)Ag}Cl. Related Au(I)NHC complexes {[Im(A)]AuCl} and {[Im(B)]AuCl} have been obtained by transmetalation using the silver carbene precursor. These compounds were characterized by several spectroscopic techniques including NMR and mass spectroscopy. HIm(B)Cl and the gold(I) complexes {[Im(A)]AuCl} and {[Im(B)]AuCl} were also characterized by X-ray crystallography. The cytotoxic properties of the NHC complexes have been assessed in various human cancer cell lines, including cisplatin-sensitive and -resistant cells. The silver(I) complex {[Im(B)](2)Ag}Cl was found to be the most active, with IC(50) values about 2-fold lower than those achieved with cisplatin in C13*-resistant cells. Growth-inhibitory effects evaluated in human nontransformed cells revealed a preferential cytotoxicity of {[Im(B)](2)Ag}Cl versus neoplastic cells. Gold(I) and silver(I) carbene complexes were also evaluated for their ability to in vitro inhibit the enzyme thioredoxin reductase (TrxR). The results of this investigation showing that TrxR appeared markedly inhibited by both gold(I) and silver(I) derivatives at nanomolar concentrations clearly point out this selenoenzyme as a protein target for silver(I) in addition to gold(I) complexes.

On/off luminescence vapochromic selective sensing of benzene and its methylated derivatives by a trinuclear silver(I) pyrazolate sensor.

{[3,5-(CF(3))(2)Pz]Ag}(3) (1) films exhibit selective/reversible sensing of small-organic-molecule (SAM) vapors, which readily switch-on bright-green (benzene or toluene) or bright-blue (mesitylene) luminescence that switches-off upon vapor removal. Vapors of electron-deficient SAMs or non-aromatic solvents did not attain luminescence switching and were not adsorbed.

A stable tridentate carbene ligand

Abstract A stable multidentate carbene ligand containing three imidazol-2-ylidenes was synthesized and characterized. The spectroscopic data suggest that there is no intramolecular interaction between the neighboring carbene sites.

Aminotroponiminato complexes of silicon, germanium, tin and lead

Abstract Aminotroponiminates are very useful ligands in group 14 chemistry. They readily form complexes with both low and high valent group 14 metal ions. Synthesis, structural features and some chemistry of aminotroponiminato silicon, germanium, tin and lead derivatives are reviewed.

Gold(I) Chloride Coordinated 3-Hexyne

A linear gold(I) complex featuring a simple, unstrained alkyne has been synthesized using AuCl and 3-hexyne and characterized using X-ray crystallography. Density functional theory calculations show that sigma donation from alkyne --> Au dominates over the Au --> alkyne pi back-donation.