ABSTRACT This paper provides the fifth manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry (For the previous manifestations, see: Comments Inorg. Chem

ABSTRACT In oxidations by nitric acid (HNO3), such as the dissolution of gold (Au) in aqua regia, mixtures of nitrogen monoxide (NO) and nitrogen dioxide (NO2) are produced. In this article, the exact processes through which these two nitrogen oxides are produced were discussed. It was shown that in the processes of dissolution in HNO3 or aqua regia, NO2 is never a direct product of oxidations by HNO3

ABSTRACT We report the effect of various Bi:Ti ratios x:1 (x = 0.5–3) on the phase formation of sodium-bismuth titanate Na0.5Bi0.5TiO3 (NBT) during hydrothermal synthesis (230°С, 3 MPa, 96 h) from titanium oxide and bismuth hydroxide in 20 M NaOH solution. It was shown that single-phase ceramics with perovskite structure could be obtained at x = 0.5–0.9 using the hot-pressing technique (1025°С, 60

ABSTRACT Objective is to investigate effect of preparation methods on crystal size at synthesis of Fe-doped TiO2 as a systematic review study. All references (455) were found by manual duplication and finally n = 136 records remained. After reading their titles, abstracts and full-texts, 58 relevant full-text articles were included based on the considered exclusion criteria. Finally, 21 relevant full-text

Metal-organic frameworks (MOFs) are of great interest to researchers in chemistry and material science due to their various chemical and physical properties, which include high surface area, augmented adsorption/desorption kinetics, biocompatibility, and functional tunability. The structurally diverse 1-D, 2-D, and 3-D metal-organic frameworks have found applications in chemical sensing and several

(2020). Advances in Organometallic Chemistry, Volume 71. Comments on Inorganic Chemistry: Vol. 40, No. 6, pp. 304-306.

Biodiesel belongs to the class of renewable and sustainable fuel sources receiving more attention as a rapidly growing field with higher potential than other energy sources. The main shortcoming of biodiesel production is the high cost of the production process and the catalytic system. The present contribution aims to briefly review and evaluate the performance of solid acid catalysts (SACs) focused

Complexes featuring metal–silicon bonds play a key role in many catalytic and stoichiometric transformations. As such, it is important to understand the underlying electronic structures of such units and the reactivity patterns they engender, which in many cases differ substantially from well-known patterns for metal–carbon bonds. This review seeks to provide a framework for understanding reactivity

In this comment, insights gained from density functional theory into the mechanism by which the Cu(I)-catalyzed boracarboxylation of vinyl arenes occurs with specific focus on the CO2 insertion step are presented. Preliminary calculations indicated a potential non-covalent interaction between boron and CO2 in the carboxylation transition state, implicating cooperative CO2 activation. A study of boron

Trinuclear coinage metal metallacycles are obtained when two-coordinate metals are bonded to C, N or N, N anionic ligands of the proper symmetry to form cycles where metals alternate with bridging ligands. Cyclotrimers often exhibit semiplanar structures and mostly columnar or finite stacking in the solid state by means of metallophilic interactions. They show some peculiar properties with an impact

BiMnO3 exhibit multiferroic properties, which attract much attention due to numerous potential applications. The most well-investigated and traditional techniques for synthesizing this material include high-pressure and high-temperature treatment. In this way, soft chemistry synthesis of BiMnO3 is desirable. Even though the formation of BiMnO3 at ambient pressure is not possible according to the phase

The selective electrochemical reduction of CO2 to value-added products is a useful strategy for the local storage of intermittent energy sources as chemical fuels and the recycling of industrial CO2 waste into industrial feedstocks. This review highlights some of the recent research focused specifically on modulating substrate delivery and local catalyst environment to enhance reaction and product

A survey of different computational approaches to compute thermochemical properties and, in particular, transition temperatures (T1/2) in spin-crossover (SCO) systems are presented. Asides from the possibility of computing accurate values, this work centers its efforts in the use of computational tools to explain trends in different families of SCO molecules. Understanding the impact that chemical

Ureas and thioureas, otherwise known as carbamides and thiocarbamides, respectively, are rich sources of nitrogen. Urea has a wide range of applications in agriculture, the chemical industry, and automobile systems, and is an important chemical in medical uses. Thiourea, an organosulfur compound, has long been known as an important reagent in organic synthesis, and has been employed in textile processing

Innovation in the development of electrochemical energy storage methods is essential if these technologies are to meet the variable needs of the electrical grid. Nonaqueous redox flow batteries represent an underdeveloped area of research in energy storage—one which has seen a recent spike in interest owing to the potential for modular, energy-dense electrochemical energy conversion. Here, we summarize

The notable progress in the field of nano-science and nano-technology addresses many environmental and energy applications. Among these, photocatalysis applications have received remarkable attention, where the TiO2 photocatalyst has great potential to play a role in the field of photocatalysis for fuel production and environmental remediation. The present review article deals with the considerable

This article provides a third manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the journal’s identity as a niche for “critical discussion” of contemporary literature in inorganic chemistry. (For the first and second manifestations, see: (1) Otten, B. M

We describe the newest approach to photodynamic therapy (PDT) using metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). PDT’s characteristic method of treating cancer as noninvasive and selective has garnered much attention. PDT has entered the realm of nanotechnology to overcome various challenges that are hindering its effectiveness. Porous materials, which are more functional

In this tutorial, we describe the applications of well-defined heterobimetallic complexes in coordination insertion polymerization catalysis. The presence of two different metals in a single catalyst platform imparts reactivity patterns that are distinct from those of their homobimetallic and monometallic counterparts. We will demonstrate that heterobimetallic complexes are a versatile and unique class

This article provides a second manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for “critical discussion of the current literature” of inorganic chemistry. (For the first manifestation, see: Otten, B. M.; Melancon, K. M

Metal-organic frameworks (MOFs) are porous molecular compositions quickly emerging as a novel electro-optical platform, especially for various energy transduction processes. Such functionalities are intimately tied with the modular MOF chemistry required for the delineation of the wide range of tunable porous structures constructed from various electrooptically active linkers and or metal nodes. Various

In this comment, we present recent insights into the mechanism of bisphosphine-iron catalyzed C(sp2)-C(sp3) cross-coupling reactions (CCRs) with the focus on the nature of the C-C bond formation event (inner-sphere versus outer-sphere) as revealed by quantum mechanical calculations from our group and others. Implications for reaction and catalyst design principles are discussed.

Iron(II)- and α-ketoglutarate-dependent (Fe/αKG) enzymes catalyze a large array of reactions. Although hydroxylation reaction catalyzed by these enzymes has been investigated in great details, involving the ferryl (FeIV=O) as a key reactive intermediate. The mechanisms of reactions other than hydroxylation are still largely unknown. By using a combined biochemical, bio-organic, and spectroscopic approach

X-ray diffraction studies on scandium salts in solution and in the solid state, have afforded Sc-O bond lengths in the ions [Sc(H2O)n]3+ (n = 6, 7 and 8) as well as for several compounds containing [(H2O)5Sc(μ-OH)2Sc(H2O)5]4+ ions. Several theoretical studies have examined different models for the aqua ion without finding agreement. This review considers these studies. Diffraction results from solutions

As the tenth year that follows the premature passing of the inorganic chemistry legend F. Albert (Al) Cotton comes to a close, we provide some soul food that we believe Al would have enjoyed as he looks down upon two generations of disciples, a grandchild and two great grandchildren, in his scientific family tree. This article also represents a new tradition by which the editors of Comments on Inorganic

Metalated three-dimensional icosahedral boron clusters often exhibit high chemical and thermal stability relative to their simple borane counterparts thus making them a convenient object to study the chemistry of metal-boron bonds. The presence of multiple reactive boron vertices makes carboranes unique ligands with unusual steric and electronic requirements. This article summarizes recent developments

Phosphorus K-edge X-ray absorption spectroscopy (XAS) is a highly effective experimental method for investigating metal-phosphorus bonding and electronic structure. Here, we provide a comprehensive review of P K-edge XAS studies of transition metal complexes and show how they were used to investigate a wide range of chemical phenomena, including covalent metal-ligand bonding, redox non-innocence in

This comment describes the available synthetic routes and some general structural features of unsupported cycloarsoxane compounds. The key synthetic strategies used to prepare this type of compound and the significant roles that they have been employed in after coordination to the metal center are fully discussed. The literature herein covers all known unsupported cycloarsoxane compounds that have

(2017). EOV Editoral Board. Comments on Inorganic Chemistry: Vol. 37, No. 6, pp. 327-327.

Magnetic carbon-based composites reside at the frontier of high-performance microwave absorbing materials (MAMs) due to their dual loss mechanisms and tunable electromagnetic properties. In this study, we review the construction of magnetic carbon-metal composites in recent years, and introduce a facile citrate-derived strategy to produce FeCo alloy/carbon composites through a direct pyrolysis of the

Over the last few decades, holmium (Ho) has been investigated for its application in laser surgery, magnetic resonance imaging, and internal and topical radionuclide therapy. Ho has a 100% natural abundance of holmium-165, which is a stable nuclide that can undergo a process called neutron-activation to generate radioactive holmium-166 (166Ho). 166Ho emits β–particles and γ photons, with a half-life

The news of Chinese traditional medicines reaching Iran suggests that these medicines are becoming increasingly available internationally. Despite the long history of the toxic effects of mercury, mercury compounds are commonly used in Chinese traditional medicines. Two mercurials contained in some Chinese traditional medicines are the salts mercury(II) sulfide (HgS) and mercury(I) chloride (Hg2Cl2)

A novel, recoverable magnetic nanocatalyst for Suzuki and Heck coupling reactions has been successfully prepared by immobilizing chitosan-bound 5-bromosalicylaldehyde Pd (II) complex on the surface of a Fe3O4 nanoparticle. Structure and composition of the solid catalyst were characterized by Fourier transform infrared (FT-IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively

(2017). Electro- and Photocatalytic Hydrogen Production by Molecular Cobalt Complexes With Pentadentate Ligands. Comments on Inorganic Chemistry: Vol. 37, No. 5, pp. 238-270.

Copper-catalyzed oxidative decarboxylative coupling reactions of benzoic acids have emerged as attractive routes to access functionalized arenes. Unfortunately, substrate scope limitations and forcing reaction conditions have prevented the widespread implementation of these methodologies. A mechanistic understanding of these systems could enable the development of more robust reactions, yet few studies

The catalytic functionalization of light alkanes, particularly methane, has attracted considerable attention from the inorganic and organic research communities for nearly five decades. The literature mechanisms for C—H activation may be divided into three broad categories: metal directed, ligand directed, or metal-ligand directed. The advantages for metal-ligand directed pathways have both steric

(2017). Hybrid Antioxidant and Metal Sequestering Small Molecules Targeting the Molecular Features of Alzheimer’s Disease. Comments on Inorganic Chemistry: Vol. 37, No. 3, pp. 146-167.

(2017). Simple Thiourea Hydrolysis or Intermediate Complex Mechanism? Taking up the Formation of Metal Sulfides from Metal–Thiourea Alkaline Solutions. Comments on Inorganic Chemistry: Vol. 37, No. 2, pp. 99-115.

(2016). Editorial Board EOV. Comments on Inorganic Chemistry: Vol. 36, No. 6, pp. ebi-ebi.

(2017). Strategies for Tuning Emission Energy in Phosphorescent Ir(III) Complexes. Comments on Inorganic Chemistry: Vol. 37, No. 3, pp. 117-145.

(2017). Hydrides of the Alkali Metals and Alkaline Earth Metals Under Pressure. Comments on Inorganic Chemistry: Vol. 37, No. 2, pp. 78-98.

(2017). On the Cu(III)/Cu(II) Redox Chemistry of Cu-Peptide Complexes to Assist Catalyst Design. Comments on Inorganic Chemistry: Vol. 37, No. 2, pp. 59-77.

(2016). Using Photoacoustic Calorimetry to Study the cis- to trans- Photoisomerization of the [Ru(II)(2,2’-bipyridine)2(H2O)2]2+ Complex in Aqueous Solution. Comments on Inorganic Chemistry: Vol. 36, No. 6, pp. 343-354.

(2017). Metal-Catalyzed and Metal-Free Intermolecular Amination of Light Alkanes and Benzenes. Comments on Inorganic Chemistry: Vol. 37, No. 1, pp. 1-57.

(2016). Coordination Chemistry of Linear Tripyrroles: Promises and Perils. Comments on Inorganic Chemistry: Vol. 36, No. 6, pp. 327-342.

(2016). Experimental and Theoretical Aspects of Anion Complexes with a Thiophene-Based Cryptand. Comments on Inorganic Chemistry: Vol. 36, No. 6, pp. 305-326.

(2016). Boron(III) Complexes with N,N’- and N,O-Heterocyclic Ligands: Synthesis and Spectroscopic Properties. Comments on Inorganic Chemistry: Vol. 36, No. 5, pp. 245-303.

(2016). Malcolm H. Chisholm – A Memoir. Comments on Inorganic Chemistry: Vol. 36, No. 4, pp. 183-195.

Electron orbitals are ubiquitous in chemistry for the description of bonding and molecular properties. This article outlines a theoretical framework for the generation and application of orbitals for the analysis of the electronic structure, chemical bonding, and magnetic properties of metal complexes from relativistic quantum chemical wavefunction calculations. Examples from the author’s research

The photovoltaic research community has been astonished by a new star: perovskite solar cells. Recent research progress in perovskite solar cells is highlighted in this review, including the crystal structures, film engineering, device performance, and future challenges.

This review focuses on the design, synthesis, and reactivity of low-coordinate base transition metal complexes supported by bulky alkoxide ligands. The unique electronic features of alkoxide ligands result in strongly electrophilic character at the metal centers, which enhances reactivity of metal-bound substrates and facilitates their transformation. However, insufficiently bulky alkoxide ligands

Biomimetic diiron complexes bearing redox non-innocent ligands are discussed in this review. The complexes are synthesized to model the active site of [FeFe] hydrogenase in order to elucidate the catalytic mechanism of H2 evolution and design superior artificial catalysts. Employment of the redox active ligands serves an important factor to modulate electronic structure of the Fe2 core as the similar

Hydrogen has emerged as a leading alternative fuel; however, efficient chemical methods for generating hydrogen from water are lacking. Thus, chemists have turned to nature for inspiration. The [NiFe] hydrogenases possess rich structural, spectroscopic, and functional properties, motivating extensive synthetic efforts to model the complex active sites. In this comment, the geometric and electronic

Density functional theory calculations reveal that the previously unreported nitrosothiol MS1 and MS2 linkage isomers are metastable species with energies similar to those determined for other experimentally observed XNO linkage isomers. Nitrosation of protein cysteines to yield S-nitrosocysteine (cySNO) is an important component of nitric oxide biology. However, high-resolution structural data of

Zeolites have been widely applied in the industrial processes and their syntheses normally require the presence of templates, structure-directing agents (SDA). The first type of SDA is inorganic cations such as sodium, and the second type is organic cations such as organic ammonium, which direct the crystallization of zeolites. In this review, we briefly summarize recent works on the organotemplate-free

The ligand 2,2’-dipyridylamine occupies a special place in modern coordination chemistry. To honor the one-hundredth anniversary of its first preparation, the chemistry of this ligand is reviewed, with a special emphasis on the structural features of the resulting metal complexes. The versatility of this ligand is manifold: it can exist in several protonation states, adopt one of nine distinct coordination

This review article summarizes recent work in developing hybrid photocatalysts by grafting molecular catalysts on solid-state surfaces for solar CO2 reduction. Several surface-immobilized systems are discussed to examine effects of ligand derivatization and surface characteristics on the activities of hybrid photocatalysts. This article also describes the extensive use of spectroscopic techniques in

Mesoporous silica nanoparticles (MSNs) have been widely explored as drug delivery vehicles in cell and animal studies. To move this nanoparticle platform into the clinic, however, further work needs to be done to predict and assess potential adverse reactions and side-effects to optimize for their efficacious and safe use in patients. Toxicity may be dependent on a number of characteristics, including

A personal perspective of Tom Ziegler’s influence on and vision of theoretical inorganic chemistry illustrated with selective but deemed representative examples taken from only one facet of the illustrious work of a great scientist.

Mechanistic aspects of olefin isomerization through an alkyl chain are discussed in this review. The mechanism primarily has been categorized in two pathways: (1) metal-hydride insertion-elimination pathway; and (2) π-allyl pathway. Different mechanistic features of the two pathways are elaborated here. These features often vary among different reaction systems. Several types of experiments, such as