Effects of Preparation Conditions on the Efficiency of Visible-Light-Driven Hydrogen Generation Based on Cd0.25Zn0.75S Photocatalysts

Photocatalytic H2 production utilizing H2S, an industrial side-product, is regarded as an environmentally friendly process to produce clean energy through direct solar energy conversion. For this purpose, sulfide-based materials, such as photocatalysts, have been widely used due to their good solar response and high photocatalytic activity. In this work, a ZnS–CdS composite was studied, and special attention was dedicated to the influence of the preparation parameters on its H2 production activity. The ZnS–CdS composite, with an enhanced photoactivity for H2 production, was synthesized both from ammine complexes and, in a conventional way, directly from acetates at various pH values. Deviating from the traditional method, the photoactivity of ZnS–CdS prepared from ammine complexes was not affected by the pH. Besides, the hydrothermal treatment and the ammonia content strongly influenced the rate of H2 production in this system. DRS, TEM, SEM, XRD, and quantum yield measurements prove the dependence of the photoactivity of these catalysts on the structural and morphological properties determined by the preparation conditions. The promising photocatalytic efficiency achieved with the application of these ZnS–CdS catalysts, prepared without any metal deposition, encourages further investigations to enhance the rate of hydrogen generation by optimization of the reaction conditions for practical utilization.

Facile N9-Alkylation of Xanthine Derivatives and Their Use as Precursors for N-Heterocyclic Carbene Complexes

The xanthine-derivatives 1,3,7-trimethylxanthine, 1,3-dimethyl-7-benzylxanthine and 1,3-dimethyl-7-(4-chlorobenzyl)xanthine are readily ethylated at N9 using the cheap alkylating agents ethyl tosylate or diethyl sulfate. The resulting xanthinium tosylate or ethyl sulfate salts can be converted into the corresponding PF6- and chloride salts. The reaction of these xanthinium salts with silver(I) oxide results in the formation of different silver(I) carbene-complexes. In the presence of ammonia, ammine complexes [Ag(NHC)(NH3)]PF6 are formed, whilst with Et2NH, the bis(carbene) salts [Ag(NHC)2]PF6 were isolated. Using the xanthinium chloride salts neutral silver(I) carbenes [Ag(NHC)Cl] were prepared. These silver complexes were used in a variety of transmetallation reactions to give the corresponding gold(I), ruthenium(II) as well as rhodium(I) and rhodium(III) complexes. The compounds were characterized by various spectroscopic methods as well as X-ray diffraction.

Activation of Ammonia and Hydrazine by Electron Rich Fe(II) Complexes Supported by a Dianionic Pentadentate Ligand Platform Through a Common Terminal Fe(III) Amido Intermediate

We report the use of electron rich iron complexes supported by a dianionic diborate pentadentate ligand system, B2Pz4Py, for the coordination and activation of ammonia (NH3) and hydrazine (NH2NH2). For ammonia, coordination to neutral (B2Pz4Py)Fe(II) or cationic [(B2Pz4Py)Fe(III)]+ platforms leads to well characterized ammine complexes from which hydrogen atoms or protons can be removed to generate, fleetingly, a proposed (B2Pz4Py)Fe(III)- NH2 complex (3Ar-NH2). DFT computations suggest a high degree of spin density on the amido ligand, giving it significant aminyl radical character. It rapidly traps the H atom abstracting agent 2,4,6-tri-tert-butylphenoxy radical (ArO•) to form a C-N bond in a fully characterized product (2Ar), or scavenges hydrogen atoms to return to the ammonia complex (B2Pz4Py)Fe(II)-NH3 (1ArNH3). Interestingly, when (B2Pz4Py)Fe(II) is reacted with NH2NH2, a fully characterized bridging diazene complex, 4Ar, is formed along with ammonia adduct 1Ar-NH3 as the spectroscopically observed (-78˚C) (B2Pz4Py)Fe(II)-NH2NH2-Fe(II)( B2Pz4Py) dimer (1Ar)2-NH2NH2 is allowed to warm to room temperature. Experimental and computational evidence is presented to suggest that (B2Pz4Py)Fe(II) induces reductive cleavage of the N-N bond in hydrazine to produce the Fe(III)-NH2 complex 3Ar-NH2, which abstracts H• atoms from (1Ar)2-NH2NH2 to generate the observed products. All of these transformations are relevant to proposed steps in the ammonia oxidation reaction, an important process for the use of nitrogen-based fuels enabled by abundant first row transition metals. <br>

Activation of Ammonia and Hydrazine by Electron Rich Fe(II) Complexes Supported by a Dianionic Pentadentate Ligand Platform Through a Common Terminal Fe(III) Amido Intermediate

We report the use of electron rich iron complexes supported by a dianionic diborate pentadentate ligand system, B2Pz4Py, for the coordination and activation of ammonia (NH3) and hydrazine (NH2NH2). For ammonia, coordination to neutral (B2Pz4Py)Fe(II) or cationic [(B2Pz4Py)Fe(III)]+ platforms leads to well characterized ammine complexes from which hydrogen atoms or protons can be removed to generate, fleetingly, a proposed (B2Pz4Py)Fe(III)- NH2 complex (3Ar-NH2). DFT computations suggest a high degree of spin density on the amido ligand, giving it significant aminyl radical character. It rapidly traps the H atom abstracting agent 2,4,6-tri-tert-butylphenoxy radical (ArO•) to form a C-N bond in a fully characterized product (2Ar), or scavenges hydrogen atoms to return to the ammonia complex (B2Pz4Py)Fe(II)-NH3 (1ArNH3). Interestingly, when (B2Pz4Py)Fe(II) is reacted with NH2NH2, a fully characterized bridging diazene complex, 4Ar, is formed along with ammonia adduct 1Ar-NH3 as the spectroscopically observed (-78˚C) (B2Pz4Py)Fe(II)-NH2NH2-Fe(II)( B2Pz4Py) dimer (1Ar)2-NH2NH2 is allowed to warm to room temperature. Experimental and computational evidence is presented to suggest that (B2Pz4Py)Fe(II) induces reductive cleavage of the N-N bond in hydrazine to produce the Fe(III)-NH2 complex 3Ar-NH2, which abstracts H• atoms from (1Ar)2-NH2NH2 to generate the observed products. All of these transformations are relevant to proposed steps in the ammonia oxidation reaction, an important process for the use of nitrogen-based fuels enabled by abundant first row transition metals. <br>

Preparation and crystal structures of the beryllium ammines [Be(NH3)4]X2 (X = Br, I, CN, SCN, N3) and Be(NH3)2X'2 (X' = Cl, Br, I)

Ammine complexes of beryllium halides and pseudo-halides have been synthesized through the reaction of metallic beryllium with ammonium salts in liquid ammonia or in the solid state.

Recent advances in the chemistry of uranium halides in anhydrous ammonia

This article presents an overview of recent advancements in the field of uranium chemistry, paying special attention to the preparation of starting materials and to the chemistry of uranium halides in liquid ammonia. Where suitable, insights into the chemistry of thorium are also presented. Herein, we report upon the crystal structures of several ammine complexes as well as their deprotonation products. Specific examples of hydrolysis products in liquid ammonia are showcased. Additionally, advancements in the preparation of uranium cyanides are presented.

How does the total charge and isomerism influence the Ru–NO ammine complexes?

The NO bioavailability is controlled from Ru–NO complexes, and thus, the influence of the total charge and ligands is explored from DFT calculations.

Crystal structure of [Ag(NH3)3]2[Ag(NH3)2]2[SnF6]F2, a compound showing argentophilic interactions

Bis[triamminesilver(I)] bis[diamminesilver(I)] hexafluoridostannate(IV) difluoride, [Ag(NH3)3]2[Ag(NH3)2]2[SnF6]F2, was obtained in the form of colourless crystals from the reaction of CsAgSnF7in anhydrous ammonia. Two different ammine complexes of silver(I) are present in the structure,i.e.a linear diammine and a T-shaped triammine complex. The ammine silver(I) complexes show Ag...Ag distances in the range of argentophilic interactions. In the crystal, several N—H...F hydrogen bonds are present between the complex cations and the SbF6−and F−anions, leading to the formation of a three-dimensional network.