Dalton Transactions

doi: 10.1039/C9DT90150Gpmid: 31268455

doi: 10.1039/c9dt90150gpmid: 31268455

doi: 10.1039/C9DT90151Epmid: 31268458

doi: 10.1039/c9dt90151epmid: 31268458

Housecroft, Catherine E.; Thomas, Christine M.; Lim, Mi Hee

doi: 10.1039/c9dt90117epmid: 31250858

Constable, Edwin C.

doi: 10.1039/c9dt00765bpmid: 30865756

The d-block elements have played an essential role in the development of our present understanding of chemistry and in the evolution of the periodic table. On the occasion of the sesquicentenniel of the discovery of the periodic table by Mendeleev, it is appropriate to look at how these metals have influenced our understanding of periodicity and the relationships between elements.

Hartshorn, Richard M.; Yerin, Andrey

doi: 10.1039/c9dt00352epmid: 30892321

This review examines the origins and development of the compositional nomenclature and additive nomenclature that have been at the heart of formal descriptions of inorganic compounds since the times of Lavoisier and Werner, respectively. The rising importance of structural diagrams is noted, explained and correlated with a decreasing use of formal nomenclature. The future of structure representation is discussed, particularly in relation to cheminformatics and big data. International variations in nomenclature are discussed with reference to the recently published Brief Guide to the Nomenclature of Inorganic Chemistry and its translations, and implications of increasing internationalisation of chemistry for the integrity of regional languages are discussed.

Hsiao, Hui-Yi; Chung, Chieh-Wei; Santos, Joshua H.; Villaflores, Oliver B.; Lu, Tsai-Te

doi: 10.1039/c9dt00777fpmid: 30990502

Iron, the most abundant transition metal ion in humans, participates in the biosynthesis, translocation, signal transduction, and transformation of nitric oxide through its encapsulation in the form of heme, [Fe–S], and [Fe(NO)2] cofactors within a variety of enzymes and proteins. After the review on nitric oxide synthase (NOS) and soluble guanylate cyclase (sGC) for the biosynthesis and detection of NO, in this report, we discuss the natural utilization of the [Fe(NO)2] motif for translocation of endogenous NO and the translational development of synthetic dinitrosyl iron complexes (DNICs) for biomedical applications. A mechanistic study of NO-release and NO-transfer reactivity of structure-characterized DNICs promoted the discovery of cell-penetrating and in vivo NO-delivery reactivity for treatment of cancer and wound healing in diabetes. Beyond activation of sGC and vasodilation, phase I/II clinical trials of glutathione-bound DNICs (Oxacom®) against hypertension encourage bioinorganic engineering of DNICs into scaffolds for tissue regeneration and repair relying on anti-bacterial, anti-inflammation, cytoprotective, and proliferative effects of NO.

Jiang, Changcheng; Nichols, Asa W.; Machan, Charles W.

doi: 10.1039/c9dt00491bpmid: 31020284

Electrocatalytic CO2 reduction is of continued interest to sustainable energy research. Mononuclear transition metal complexes from Group 6 to Group 10 with a select subset of ligand frameworks have been demonstrated to be efficient electrochemical CO2 reduction catalysts. Here, we review the known mononuclear complexes from Group 6 to Group 10, examining trends in activity, electronic structure of catalytic intermediates, and product selectivity. The correlation between differences in electronic structure and CO2 reduction activity between these metal centers are discussed.

Fukuzumi, Shunichi; Lee, Yong-Min; Nam, Wonwoo

doi: 10.1039/c9dt01402kpmid: 31112168

In the first-row of d-block metals, ten elements are included, such as scandium (Sc, 3d1), titanium (Ti, 3d2), vanadium (V, 3d3), chromium (Cr, 3d54s1), manganese (Mn, 3d5), iron (Fe, 3d6), cobalt (Co, 3d7), nickel (Ni, 3d8), copper (Cu, 3d104s1) and zinc (Zn, 3d10). The synthesis, characterization, and reactivity of first-row d-block metal-superoxo complexes are discussed together with the structures of the end-on (η1) and side-on (η2) metal-superoxo complexes in this review article. Electron transfer from electron donors to O2 is enhanced by binding of Sc3+ to produce an end-on type Sc(iii)-superoxo complex. Metal-superoxo complexes such as Ti(iv)-superoxo, oxovanadium(v)-superoxo, Cr(iii)-superoxo, Fe(iii)-superoxo, Co(iii)-superoxo, Ni(iii)-superoxo and Cu(ii)-superoxo species generally undergo hydrogen atom transfer reactions. A Cr(iii)-superoxo complex undergoes not only hydrogen atom transfer but also oxygen atom transfer reactions. In the presence of protons (e.g., trifluoromethanesulfonic acid, HOTf), much enhanced acid catalysis was observed in oxygen atom transfer reactions from a nonheme Cr(iii)-superoxo complex, [(Cl)(TMC)CrIII(O2)]+, to thioanisole. The enhanced reactivity of [(Cl)(TMC)CrIII(O2)]+ by HOTf results from proton-coupled electron transfer (PCET) from electron donors, including thioanisole, to [(Cl)(TMC)CrIII(O2)]+. A manganese(iv)-superoxo complex plays a very important role in thermal and photoinduced dioxygen activation by a Mn(iii) corrolazine complex. A metal-superoxide complex using the last element in the first-row of transition metals, that is a Zn(ii)-superoxide complex, is produced to accelerate the reduction of O2˙− in a SOD (superoxide dismutase) model.