Zinc borylation and reduction by a diborane(4) species B-O bond formation.

We report a convenient synthesis of the zinc-boryl complex (Nacnac)ZnBpin under mild conditions formal disproportionation of bis(pinacolato)diboron(4), aided thermodynamically by B-O bond formation. This species can be isolated both base-free and as the DMAP adduct (Nacnac)Zn(DMAP)Bpin and crystallographically characterised in the latter form. Onward reactivity of the base free zinc boryl complex with CO occurs reductively, yielding further B-O bonds as well as CO gas.

Mechanistic investigations of the Fe(ii) mediated synthesis of squaraines.

The scission and homologation of CO is a fundamental process in the Fischer-Tropsch reaction. However, given the heterogeneous nature of the catalyst and forcing reaction conditions, it is difficult to determine the intermediates of this reaction. Here we report detailed mechanistic insight into the scission/homologation of CO by two-coordinate iron terphenyl complexes.

Fe-Fe bonding in the rhombic Fe cores of the Zintl clusters [FeE] (E = Sn and Pb).

We report here the synthesis and characterization of two endohedral Zintl-ion clusters, [FeSn] and [FePb], which contain rhombic Fe cores. The Fe-Fe bond lengths are all below 2.5 Å, distinctly shorter than in the corresponding Cu clusters, indicating the presence of Fe-Fe bonding.

Electrochemical Nanoreactor Provides a Comprehensive View of Isocitrate Dehydrogenase Cancer-drug Kinetics.

The ability to control enzyme cascades entrapped in a nanoporous electrode material (the "Electrochemical Leaf", e-Leaf) has been exploited to gain detailed kinetic insight into the mechanism of an anti-cancer drug. Ivosidenib, used to treat acute myeloid leukemia, acts on a common cancer-linked variant of isocitrate dehydrogenase 1 (IDH1 R132H) inhibiting its "gain-of-function" activity-the undesired reduction of 2-oxoglutarate (2OG) to the oncometabolite 2-hydroxyglutarate (2HG). The e-Leaf quantifies the kinetics of IDH1 R132H inhibition across a wide and continuous range of conditions, efficiently revealing factors underlying the inhibitor residence time.

Snap-shots of cluster growth: structure and properties of a Zintl ion with an Fe core, [FeSn].

The endohedral Zintl-ion cluster [FeSn] contains a linear Fe core with short Fe-Fe bond lengths of 2.4300(9) Å. The ground state is a septet, with significant σ and π contributions to the Fe-Fe bonds.

Redox tuning of the H-cluster by second coordination sphere amino acids in the sensory [FeFe] hydrogenase from .

[FeFe] hydrogenases are exceptionally active catalysts for the interconversion of molecular hydrogen with protons and electrons. Their active site, the H-cluster, is composed of a [4Fe-4S] cluster covalently linked to a unique [2Fe] subcluster. These enzymes have been extensively studied to understand how the protein environment tunes the properties of the Fe ions for efficient catalysis.

Binding of exogenous cyanide reveals new active-site states in [FeFe] hydrogenases.

[FeFe] hydrogenases are highly efficient metalloenyzmes for hydrogen conversion. Their active site cofactor (the H-cluster) is composed of a canonical [4Fe-4S] cluster ([4Fe-4S]) linked to a unique organometallic di-iron subcluster ([2Fe]). In [2Fe] the two Fe ions are coordinated by a bridging 2-azapropane-1,3-dithiolate (ADT) ligand, three CO and two CN ligands, leaving an open coordination site on one Fe where substrates (H and H) as well as inhibitors ( O, CO, HS) may bind.

Synthesis and characterisation of the ternary intermetalloid clusters {M@[As(ZnMes)]} (M = Nb, Ta) from binary [M@As] precursors.

The development of rational synthetic routes to inorganic arsenide compounds is an important goal because these materials are finding applications in many areas of materials science. In this paper, we show that the binary crown clusters [M@As] (M = Nb, Ta) can be used as synthetic precursors which, when combined with ZnMes, generate ternary intermetalloid clusters with 12-vertex cages, {M@[As(ZnMes)]} (M = Nb, Ta). Structural studies are complemented by mass spectrometry and an analysis of the electronic structure using DFT.

Coinage metal aluminyl complexes: probing regiochemistry and mechanism in the insertion and reduction of carbon dioxide.

The synthesis of coinage metal aluminyl complexes, featuring M-Al covalent bonds, is reported a salt metathesis approach employing an anionic Al(i) ('aluminyl') nucleophile and group 11 electrophiles. This approach allows access to both bimetallic (1 : 1) systems of the type ( BuP)MAl(NON) (M = Cu, Ag, Au; NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di--butyl-9,9-dimethylxanthene) and a 2 : 1 di(aluminyl)cuprate system, K[Cu{Al(NON)}]. The bimetallic complexes readily insert heteroallenes (CO, carbodiimides) into the unsupported M-Al bonds to give systems containing a M(CE)Al bridging unit (E = O, NR), with the μ-κ(C):κ(E,E') mode of heteroallene binding being demonstrated crystallographically for carbodiimide insertion in the cases of all three metals, Cu, Ag and Au.

Selective propargylic C(sp)-H activation of methyl-substituted alkynes [2 + 2] cycloaddition at a titanium imido template.

The reaction of the titanium imido complex with 2-butyne leads to the formation of the titanium azadiene complex at ambient temperature instead of yielding the archetypical [2 + 2] cycloaddition product (titanaazacyclobutene) which is usually obtained by combining titanium imido complexes and internal alkynes. The formation of is presumably caused by an initial propargylic C(sp)-H activation step and quantum chemical calculations suggest that the outcome of this unexpected reactivity is thermodynamically favored. The previously reported titanaazacyclobutene (which is obtained by reacting with 1-phenyl-1-propyne) undergoes a rearrangement reaction at elevated temperature to give the corresponding five-membered titanium azadiene complex .

Supertetrahedral polyanionic network in the first lithium phosphidoindate LiInP - structural similarity to LiSiP and LiGeP and dissimilarity to LiAlP and LiGaP.

Phosphide-based materials have been investigated as promising candidates for solid electrolytes, among which the recently reported LiAlP displays an ionic conductivity of 3 mS cm. While the phases Li-Al-P and Li-Ga-P have already been investigated, no ternary indium-based phosphide has been reported up to now. Here, we describe the synthesis and characterization of the first lithium phosphidoindate LiInP, which is easily accessible ball milling of the elements and subsequent annealing.

Single-step synthesis and interface tuning of core-shell metal-organic framework nanoparticles.

Control over the spatial distribution of components in metal-organic frameworks has potential to unlock improved performance and new behaviour in separations, sensing and catalysis. We report an unprecedented single-step synthesis of multi-component metal-organic framework (MOF) nanoparticles based on the canonical ZIF-8 (Zn) system and its Cd analogue, which form with a core-shell structure whose internal interface can be systematically tuned. We use scanning transmission electron microscopy, X-ray energy dispersive spectroscopy and a new composition gradient model to fit high-resolution X-ray diffraction data to show how core-shell composition and interface characteristics are intricately controlled by synthesis temperature and reaction composition.

Facile reductive synthesis of both nitrogen deficient and protonated g-CN nanosheets for the synergistic enhancement of visible-light H evolution.

A new strategy is reported here to synthesize both nitrogen deficient and protonated graphitic carbon nitride (g-CN) nanosheets by the conjoint use of NHCl as a dynamic gas template together with hypophosphorous acid (HPO) as a doping agent. The NHCl treatment allows for the scalable production of protonated g-CN nanosheets. With the corresponding co-addition of HPO, nitrogen vacancies, accompanied by both additional protons and interstitially-doped phosphorus, are introduced into the g-CN framework, and the electronic bandgap of g-CN nanosheets as well as their optical properties and hydrogen-production performance can be precisely tuned by careful adjustment of the HPO treatment.