Themed collection New Talent: Americas

Welcome to this themed issue of Dalton Transactions entitled ‘2016 New talent Americas across academia and the U.S. National Laboratories’ guest edited by Professor John Arnold, Dr James Boncella, Professor Pingyun Feng, Dr Tina M. Nenoff, and Professor Christine Thomas.

Recent advances in biomimetic catalysis of MOFs have been summarized and reviewed.

In situ assembly of a heterobimetallic Pt–Ti catalyst from a titanium-containing phosphinoamide ligand enables fast room temperature catalysis in enyne cycloisomerization reactions.

Net hydride abstraction of a pincer-ligated iridium dihydride was accomplished by electrochemical oxidation (as H⁺/2e⁻) and chemical hydride transfer (as H⁻).

The syntheses of the first carboranyl N-heterocyclic carbene complexes with transition metals are reported.

A bis(phosphine)/triflatosilyl pincer-type Rh(I) complex can reversibly store one equivalent of H₂ across the Si–Rh bond upon triflate migration from silicon to rhodium.

Permanently porous hydrogen-bonded organic frameworks comprising rod-like molecules with two MIDA boronate termini have been prepared.

DFT calculations were performed in an effort to evaluate the mechanism of O₂ insertion into the Pt–H bond of Tp^Me₂Pt^IVMe₂H catalyzed by AIBN or light.

A double-well exists along the ruffling coordinate of cyanide-inhibited ferric heme, which explains the observation of “nested” VTVH MCD saturation magnetization curves.

Ligand K-edge XAS and DFT studies of ligand variations in Rh(I) pincer complexes and correlations to small molecule reactivity.

The reactivity of thorium–phosphido and thorium–arsenido bonds was probed using tert-butyl isocyanide, ^tBuNC.

The defect chemistry of Cr-doped SrTiO₃ is modified through a simple chemical reduction route to increase the Cr³⁺ dopants in the lattice.

This effort describes the isolation of a persistent Mo(I) monoiodide complex and its conversion to an unusual set of divalent (PDI)Mo complexes.

Hydride transfer from a molecular nickel hydride to CO₂ changes from unfavourable in organic solvent to favourable in aqueous solution.

A rare non-square-planar mononuclear Cr(II) bis(alkoxide) complex Cr(OR′)₂(THF)₂ is reported and its reactivity with organic carbonyls and CO₂ is investigated.

Alginate hydrogels are suitable for the encapsulation of biomolecules and microorganisms for the building of bioactive materials.

Crystallization kinetics of a promising phase change material are revealed with advanced photo-emission transmission electron microscopy with nanosecond-scale time resolution.

Traverse the EC′ Zone Diagram with a molecular H₂-evolving electrocatalyst through systematic variation of the acid pK_a, scan rate, acid concentration and catalyst concentration.

Homoleptic bis(imino)acenaphthene complexes of aluminum, chromium, and gallium were synthesized, characterized and modeled to compare the orbital contributions of main group elements and transition metals in ligand-based redox events toward increasing energy density of battery electrolytes.

An iridium complex supported by a PC^PyP ligand featuring an internal pyridine tether showed selective mono-C–H activation of ethers, which represent intermediates in the synthesis of the corresponding Fischer carbenes.

The electronic structure in the complete series of stable lanthanide sesquioxides, Ln₂O₃ (Ln = La to Lu, except radioactive Pm), has been evaluated using oxygen K-edge X-ray absorption spectroscopy with a scanning transmission X-ray microscope (STXM).

Tripodal ligands designed to generate a local C₃ symmetry have resulted in novel types of metal complexes that feature unusual bonding and electronic properties.

Multidentate chromophore-bearing ligands are used to sensitize luminescence emission from trivalent americium, providing insight on the resulting complex coordination properties.

Carbonate additives enhance the activity of [Cp*Ir(H₂O)₃](OTf)₂ for non-directed C–H activations and the aerobic C–H oxygenation of alkyl arenes.

Effect of the thermal treatment temperature on the photoelectrochemical (PEC) activity of CdSe/TiO₂ nanocomposites.

Zr_1−xSi_xO₂ mesoporous oxide thin films were obtained and their interdispersion was demonstrated by careful characterization using spectroscopic techniques.

Surface evolution of a nano-catalyst comprised of oxidized Co NPs and MgO nano-plates was studied under O₂, H₂ and H₂ + CO atmospheres using synchrotron-based X-ray spectroscopies.

The reactions of molecules containing E–H functionalities (E = Group 15 or 16 element) and pentaphenylborole were investigated revealing diverse outcomes.

The synthesis of a full series of group 4/nickel complexes supported by a 2-(diphenylphosphino)pyrrolide (NP) ligand is reported.

Robust and highly transparent quasi amorphous ZrO₂-water-glycerol hydrogels were obtained in a mild one pot procedure, based on the 2,3-epoxy-1-propanol driven alkalinization.

Five heteroleptic Cu(I)bis(phenanthroline) chromophores with distinct variation in the steric bulk at the 2,9-phenanthroline position were synthesized using the HETPHEN method, and their ground and excited state properties are described.

In this paper, a rigid scaffold imposes the photophysics of chromophores with a benzylidene imidazolidinone core by mimicking the β-barrel structure of the green fluorescent protein (GFP) and its analogs.

The Tolman electronic parameters (TEP) and cone angles were experimentally measured for a series of substituted proazaphosphatranes ligands by synthesizing their respective Ni(L^R)(CO)₃ complexes, where L = P(RNCH₂CH₂)₃N and R = Me, iPr, iBu and Bz.

A series of monomeric silylchalcogenolate ligand salts, stabilized by the [K(18-crown-6)]⁺, cation have been prepared and isolated in good yields, along with full structural and spectroscopic characterization.

Transition metal heterobimetallic complexes with dative metal–metal interactions have the potential for novel fast reactivity.

Hindered N- or P-donors have been grafted onto an N-heterocyclic olefin scaffold and versatile coordination behavior involving this new ligand set is described.

[Ni(P^Cy₂N^Arginine₂)₂]²⁺ (CyArg) or [Ni(P^Cy₂N^Benzyl₂)₂]²⁺ (CyBn) were evaluated for H₂ oxidation as a function of temperature, pressure, and solvent. 70 °C and 100 atm H₂ result in a TOF of 1.1 × 106 s⁻¹ and an overpotential of 240 mV for CyArg in water. In methanol the rates were 280 s⁻¹ for CyArg and 80 s⁻¹ for CyBn, demonstrating the importance of water and the outer coordination sphere (OCS).

The thermal degradation mechanism of triangular Ag@SiO₂ nanoparticles is elucidated through extended X-ray absorption fine structure measurements.

We have synthesized the first diamidocarbene (DAC)-supported borenium salt which was found to readily undergo two sequential 1-electron reductions to give a boryl-substituted DAC-centred radical and a DAC-supported aminoborylene.

First principles molecular dynamics simulation reveals the structure and solvation of the Ca₂UO₂(CO₃)₃ complex in water and the hydrogen bonding network that differentiates the two Ca ions.

The synthesis and characterization of a series of cobalt complexes featuring a pincer bis(carbene) ligand of the meta-phenylene-bridged bis-N-heterocyclic carbene (^ArCCC, Ar = 2,6-diispropylphenyl or mesityl) are reported.

Ethylene glycol can complex with titanium alkoxide to yield a chelated and stabilized titanium glycolate species that can be used as an excellent precursor for coating nanoscale colloidal objects. The titanium glycolate coating can be converted to crystalline TiO₂ either through high temperature calcination or refluxing in water.

An electrocatalytically active cobalt diimine dioximate metalloligand was prepared and explored as a precursor for a variety of multimetallic complexes with Co–Zn, –Cd, –Mn, and –Ru coordination.