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The influence of heterometals on dinitrogen binding at synthetic iron-sulfur clusters

Of the three nitrogenase isozymes (Mo, V, and Fe-only), the Mo nitrogenase shows the highest selectivity for N2 vs. H+ reduction. Here, we study the reduction chemistry of a series of synthetic [MFe3S4] clusters and find that only those that contain large auxiliary metals bind N2 at Fe. These results support an electronic role for “heterometals” featuring diffuse orbitals in facilitating N2 binding at neighboring Fe sites.

dlvr.it

Molybdenum doping enhances backbonding at neighboring iron centers in iron-sulfur clusters

Why is the Mo nitrogenase more adept at N2 reduction than its alternative nitrogenase counterparts (V and Fe-only)? To investigate this question, we undertook a comparative structural and spectroscopic analysis of synthetic [MoFe3S4] and [Fe4S4] clusters. We found differences in how the clusters distribute electron density, with the iron centers in the [MoFe3S4] clusters being better at backbonding to weakly π-acidic ligands. Such differences may account for the greater efficiency of the Mo nitrogenase.

dlvr.it

An isolable nitrene radical anion as a nucleophilic open-shell nitrogen synthon

Nitrenes are well-known reactive intermediates used to form a variety of nitrogen-containing molecules, but their reduced radical anions have remained inaccessible under ambient temperature. Here, a persistent nitrene can be converted into an isolable radical anion that features a non-Aufbau electronic configuration. This species acts as a nucleophilic nitrogen radical that forms new N–Se, N–Si, and N–C bonds under mild conditions.

dlvr.it

Electronic Structures of Pt(0) Complexes and Atomically Precise Clusters from Solid-State 195Pt NMR Signatures

Metal clusters are of broad interest across fields in that they possess unique properties making them appealing for a variety of applications; additionally, they provide fundamental understanding of t...

pubs.acs.org

A neutral σ0π2 carbene enabling hydrogen activation via a σ-face pathway - Nature Chemistry

Hydrogen activation by stable carbenes is rare and typically proceeds through π-face, non-least-motion pathways. Now, a neutral σ0π2 carbene has been synthesized and shown to cleave H2 at room tempera...

nature.com

A Simple, Air Stable Single-Ion Source of Iron(I)

Molecular complexes of iron in the rare +1 oxidation state have been shown to be efficient catalysts for industrially relevant chemical transformations, typically associated with the increasingly unsu...

pubs.acs.org

Modular Design Enables Access to Onium‐Substituted Diphosphacyclobutadienyl Complexes

A modular synthetic approach affords a series of cationic cobalt and manganese carbonyl half-sandwich complexes bearing onium-substituted diphosphacyclobutadienyl ligands. In this strategy, the onium....

chemistry-europe.onlinelibrary.wiley.com

Molecular low-oxidation-state chemistry with tetra-anionic group 14 elements - Nature Synthesis

Using a hydrocarbon-soluble Mg0 complex, the heavier tetrel elements silicon, germanium, tin and lead are reduced to their ultimate negative oxidation state −IV. Despite fulfilling the octet rule, tet...

nature.com

Pentasilacyclopentadienide: A Hückel aromatic species at the border of resonance and equilibrium

Aromatic rings such as the ubiquitous π-ligand cyclopentadienide (C5H5−) adhere to the famous Hückel rule with their 4n+2 π cyclically delocalized electrons. Since the advent of stable Si–Si π-bonds i...

science.org

Al(II) Transfer Harnessing a Well-Defined Cadmium Precursor

Low-valent aluminum chemistry continues to expand the boundaries of main-group reactivity, yet the selective generation and transfer of Al(II) fragments remain underexplored. Controlled Al(II) transfe...

pubs.rsc.org

GitHub - TaminoCairoli/CubeNTube: A simple plugin that extends the eraser functionality of ChimeraX. It provides a cube, a cylinder and a custom shape eraser. The eraser tools are available in the Rig...

A simple plugin that extends the eraser functionality of ChimeraX. It provides a cube, a cylinder and a custom shape eraser. The eraser tools are available in the Right Mouse toolbar. - TaminoCairo...

github.com

Silicon cyclopentadienides featuring a nonplanar 6π aromatic Si5 ring

Compared with the wide variety of reports on carbon π-electron compounds, the silicon counterparts remain scarce because of the intrinsic preference of silicon to form σ-bonded compounds. In particula...

science.org

Aluminium redox catalysis enables cyclotrimerization of alkynes - Nature

Aluminium redox catalysis is achieved with a low-valent aluminium species, carbazolylaluminylene, enabling cyclotrimerization of alkynes and producing diverse benzene derivatives.

go.nature.com

Crystalline nitrogen chain radical anions - Nature Chemistry

The isolation of catenated nitrogen compounds is difficult, in part because these chains can readily lose nitrogen, creating a strong thermodynamic push towards decomposition. Now, a series of molecul...

nature.com

Isolable Cuprocenes: Bis(tri-tert-butylcyclopentadienyl) Complexes of Copper

Seventy years after the discovery of ferrocene, the first neutral bis(cyclopentadienyl)metal complex of copper has been synthesized: Cpttt2Cu, 1 (Cpttt = C5H2tBu3). Comparison of this compound and the...

pubs.acs.org

Ferrioxalate photocatalysis: A multitasking platform for reductive iron catalysis

Iron’s abundance motivates its use in sustainable catalyst systems that also offer complementary reactivity manifolds compared to precious metals. However, the challenging reduction of benchmark iron ...

science.org

Disentangling First and Second Sphere Effects in Iron–Sulfur Cubanes

Cubane-type iron–sulfur clusters (Fe4S4) are some of the most versatile metallocofactors and, as such, among multiple functions, primarily responsible for mediating challenging electron transfers (ETs...

pubs.acs.org

Seven-Coordinate Lanthanide Bis-Halide Bis-Tetrathiometallate Complexes: A Compelling Platform for Luminescent and Magnetic Properties

To harness the unique luminescent and magnetic properties of lanthanides, precise control over their coordination sphere is essential, whether to minimize deactivation processes or maximize magnetic a...

pubs.acs.org