Organometallic chemistry articles within Nature Communications

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  • Article
    | Open Access

    Chiral 1,4-dienes are versatile building blocks in asymmetric synthesis, therefore their production is highly sought after. Here, the authors report an efficient enantioselective cross-hydroalkenylation of cyclic 1,3-dienes and terminal olefins affording chiral 1,4-dienes by using a chiral NHC-Ni(allyl)]BArF catalyst.

    • Yang Chen
    • , Liang Dang
    •  & Chun-Yu Ho

  • Article
    | Open Access

    Realizing efficient blue-emitting organic light-emitting diodes (OLEDs) with long operational lifetime is key to the development of future display technologies. Here, the authors report efficient host-guest and host-free OLEDs featuring designed carbene-metal-amide-type deep-blue photoemitters.

    • Patrick J. Conaghan
    • , Campbell S. B. Matthews
    •  & Alexander S. Romanov

  • Article
    | Open Access

    Metal-ligand δ and φ interactions, though considered weak, may be necessary for fully describing the electronic and geometric structures of certain compounds. Here, in actinide metallacycles, the authors discover two new types of M-L δ and φ back-bonds that contribute substantially to their unusual chemical behavior.

    • Morgan P. Kelley
    • , Ivan A. Popov
    •  & Ping Yang

  • Article
    | Open Access

    Electron spin is a fundamental property of molecules, and changes in spin state affect both molecular structure and dynamics. Here, the authors resolve, by ultrafast electron diffraction, the nuclear reorganization stabilizing spin transitions in a [FeII(bpy)3](PF6)2 crystal.

    • Yifeng Jiang
    • , Lai Chung Liu
    •  & R. J. Dwayne Miller

  • Article
    | Open Access

    Transition metal-catalysed C–H hydroxylation is one of the most notable synthetic advances to access alcohols and phenols. Here, the authors report a metal-free, mild C–H hydroxylation of (hetero)arenes via boron-mediated chelation.

    • Jiahang Lv
    • , Binlin Zhao
    •  & Zhuangzhi Shi

  • Article
    | Open Access

    The development of cost-effective, sustainable, and efficient catalysts for liquid organic hydrogen carrier systems is a significant goal. Herein, authors present a system based on manganese catalysis with a theoretical H2 capacity of 5.3 wt% and high selectivity for the dehydrogenation reaction.

    • Zhihui Shao
    • , Yang Li
    •  & Qiang Liu

  • Article
    | Open Access

    Molecules can serve as biomimetic sensors, but dual self-controlling systems that involve self-activation and self-regulation are difficult to mimic. Here the authors report an insulated conjugated bimetallopolymer with cooperative multiple transition metals that phosphoresces in response to carbon monoxide.

    • Hiroshi Masai
    • , Takuya Yokoyama
    •  & Jun Terao

  • Article
    | Open Access

    Chlorine evolution reaction (CER) is a key electrochemical reaction for chemical, pulp, and paper industries, and water treatments. Here, the authors report that an atomically dispersed Pt−N4 site can catalyse CER with high activity and selectivity under a wide range of Cl– concentrations and pH.

    • Taejung Lim
    • , Gwan Yeong Jung
    •  & Sang Hoon Joo

  • Article
    | Open Access

    Fast intermetallic electron transfer is expected in principle in nanozised transition metal complexes, but has been prevented by the bridging ligands. Here the authors synthesize a mixed-valence iron metal-ligand nanocluster with cyanide bridges, showing extended delocalized electronic structure

    • Wei Huang
    • , Shuqi Wu
    •  & Osamu Sato

  • Article
    | Open Access

    Low dimensional lead halide perovskites possess intriguing optical properties that are still under debate. Here Cui et al. use hydrogen bonds containing spacers to synthesize highly luminescent perovskites with fully isolated lead-bromide octahedras and shed light on the origin of the emission.

    • Bin-Bin Cui
    • , Ying Han
    •  & Qi Chen

  • Article
    | Open Access

    Extending the π‐conjugation of phthalocyanine dyes, while synthetically challenging, has the potential to produce desirable new molecular materials. Here, the authors use a templated on‐surface approach to synthesize several extended phthalocyanine derivatives from the same building block, including a lanthanide superphthalocyanine and an open‐chain polycyanine.

    • Qitang Fan
    • , Jan-Niclas Luy
    •  & J. Michael Gottfried

  • Article
    | Open Access

    Copper-oxygen species in organometallic complexes and enzymes are involved in many oxidation reactions. Here, the authors synthesize a macrocycle-protected mixed valence Cu(I/II) cluster with an unusually strong oxidation capacity and apply it to hydrogen atom transfer reactions with inert hydrocarbons.

    • Siqi Zhang
    •  & Liang Zhao

  • Article
    | Open Access

    While main group elements possess four valence orbitals that are accessible for bonding, quadruple bonding to main group elements is very rarely observed. Here the authors report that boron is able to form four bonding interactions with iron in the BFe(CO)3- anion complex.

    • Chaoxian Chi
    • , Jia-Qi Wang
    •  & Jun Li

  • Article
    | Open Access

    Little is known about interactions between two antiaromatic molecules. Here, the authors synthesised a cyclophane, in which two antiaromatic porphyrin moieties adopt a stacked face-to-face geometry with a distance shorter than the sum of the van der Waals radii of the atoms involved.

    • Ryo Nozawa
    • , Jinseok Kim
    •  & Hiroshi Shinokubo

  • Article
    | Open Access

    The study of main group complexes remains important to our fundamental understanding of main group element bonding and properties. Here the authors isolate and spectroscopically characterize a series of 8-coordinated alkaline earth metal–dinitrogen complexes M(N2)8 (M=Ca, Sr, Ba) in a low-temperature neon matrix.

    • Qian Wang
    • , Sudip Pan
    •  & Gernot Frenking

  • Article
    | Open Access

    Lanthanide sandwich complexes represent both a fundamental class of organometallic compounds and promising molecular magnets for information storage. Here the authors unveil a class of lanthanide sandwich complexes containing fully π-coordinated 8- and 9-membered rings, and show their slow relaxation of the magnetization.

    • L. Münzfeld
    • , C. Schoo
    •  & P. W. Roesky

  • Article
    | Open Access

    Studying the electronic structures and spin transitions of synthetic heme analogs is crucial to advancing our understanding of heme enzyme mechanisms. Here the authors show that a Co(II) porphyrin complex undergoes an unexpected spin state transition upon deprotonation of its axial imidazole ligand.

    • Jianping Zhao
    • , Qian Peng
    •  & Jianfeng Li

  • Article
    | Open Access

    Coordination complexes based on polydentate ligands that contain both nitrogen and carbon ligating atoms are ubiquitous, but design of those with planar cores remains challenging. Here the authors show that complexes with planar CCCN, CCCCN and NCCCN cores can be accessed by modification of the coordinating atoms in CCCC core complexes.

    • Xiaoxi Zhou
    • , Xin Pang
    •  & Haiping Xia

  • Article
    | Open Access

    Carbonyl complexes have been studied extensively thanks to their rich substitution and redox chemistry, but most homoleptic transition metal carbonyl complexes isolated in the condensed phase are neutral or anionic. Here, the authors isolate two homoleptic carbonyl radical cations in the condensed phase; both 17-electron [Cr(CO)6]•+ salts.

    • Jan Bohnenberger
    • , Wolfram Feuerstein
    •  & Ingo Krossing

  • Article
    | Open Access

    Dilanthanide complexes that possess radical bridges exhibit enhanced magnetic exchange coupling, affording molecular magnets with high blocking temperatures. Here, the authors explore a series of dilanthanide-encapsulated fullerenes where the radical bridge is taken to its limit and the role is played by a single unpaired electron.

    • Fupin Liu
    • , Georgios Velkos
    •  & Alexey A. Popov

  • Article
    | Open Access

    While chemical bonding between carbon and the d- and p-block elements is relatively well-studied, that between carbon and the f-block elements remains comparatively poorly understood. Here, the authors synthesize a series of uranium−carbone complexes in which carbon forms an unprecedented double dative bond to uranium.

    • Wei Su
    • , Sudip Pan
    •  & Congqing Zhu

  • Article
    | Open Access

    Controlled switching of the spin state of transition metal ions is key in many enzymatic reactions, but difficult to replicate in synthetic systems. Here the authors report on an iron(III) porphyrin with a photochromic axial ligand that, in solution, reversibly switches between low-spin and high-spin upon irradiation with two different wavelengths.

    • Sreejith Shankar
    • , Morten Peters
    •  & Rainer Herges

  • Article
    | Open Access

    Hyperpolarization methods play a crucial role in the in vivo observation of molecular metabolism by MRI techniques. Here, the authors develop NHC-containing iridium complexes which improve the NMR detectability of 1H, 13C and 15N nuclei via transfer of latent magnetism of para-hydrogen into a substrate.

    • Peter J. Rayner
    • , Philip Norcott
    •  & Simon B. Duckett

  • Article
    | Open Access

    The mechanism for nickel-catalyzed catalyst transfer polycondensation of thiophenes to polythiophenes. Here the authors show experimental and computational evidence of structurally characterized square planar η2-Ni(0)–thiophene species and their relevance to the mechanism of catalyst transfer polycondensation.

    • Weiying He
    • , Brian O. Patrick
    •  & Pierre Kennepohl

  • Article
    | Open Access

    Configuring surfaces on-demand for desired functionalities is an ongoing challenge. Here, diverse and tailorable modifications of quartz and porous silica surfaces that are rapidly and reversibly switchable by the use of visible light are achieved via ruthenium-thioether coordination.

    • Chaoming Xie
    • , Wen Sun
    •  & Si Wu

  • Article
    | Open Access

    Metal-mediated activation of CO for C-C coupling reactions is a valuable approach to carbon monoxide valorization. Here, the authors use low-coordinate iron(II) complexes for the selective scission and homologation of CO affording unusual squaraines and iron carboxylates under mild conditions.

    • Helen R. Sharpe
    • , Ana M. Geer
    •  & Deborah L. Kays

  • Article
    | Open Access

    Nitrogenase—whose cofactor consists of a metal–sulfur cluster—catalyzes the production of NH3 from N2, but designing metal–sulfur complexes capable of promoting this conversion remains challenging. Here, the authors report on the activation of N2 by a metal–sulfur cluster containing [Mo3S4Ti] cubes, demonstrating NH3 and N2H4 production.

    • Yasuhiro Ohki
    • , Keisuke Uchida
    •  & Takehiro Ohta

  • Article
    | Open Access

    While polyhedral boron hydride complexes have found application in a number of diverse fields, the isolation of stable aluminium analogues remains highly challenging. Here, Jones and colleagues demonstrate that reduction of an amidinato-aluminum(III) hydride complex with magnesium(I) dimers affords stable aluminium(I) hydride compounds.

    • Simon J. Bonyhady
    • , David Collis
    •  & Cameron Jones

  • Article
    | Open Access

    Owing to the propensity for uranium(III) compounds to undergo disproportionation, uranium-element multiple bonds involving uranium(III) oxidation states remain rare. Here the authors report hexauranium-methanediide rings that formally contain uranium(III)- and uranium(IV)-methanediides supported by alternating halide and arene bridges.

    • Ashley J. Wooles
    • , David P. Mills
    •  & Stephen T. Liddle

  • Article
    | Open Access

    Transition-metal catalysis in living cells poses numerous challenges in terms of biocompatibility, and complex stability and reactivity. Here, the authors report a bioorthogonal gold-catalyzed C-C coupling reaction, occurring in living mammalian cells, even in parallel with a ruthenium-catalyzed deallylation reaction.

    • Cristian Vidal
    • , María Tomás-Gamasa
    •  & José L. Mascareñas

  • Article
    | Open Access

    Attempts to bend and twist multiple bonds in order to alter their reactivities have thus far been met with only modest success. Here, Braunschweig and colleagues isolate double-bond-containing boron-based species and their 90°-twisted diradical analogs, thanks to their stabilization with Lewis basic units.

    • Julian Böhnke
    • , Theresa Dellermann
    •  & Holger Braunschweig

  • Article
    | Open Access

    The development of molecular catalysts for the reverse water–gas shift reaction is impeded by the general selectivity of CO2 insertion into M–H bonds to formates. Here, the authors report that the selectivity of CO2 insertion into a Ni–H bond can be inverted from normal to abnormal insertion upon switching from thermal to photochemical conditions.

    • Felix Schneck
    • , Jennifer Ahrens
    •  & Sven Schneider

  • Article
    | Open Access

    MRI contrast agents containing the rare earth metal gadolinium are very effective, yet unstable and thus potentially hazardous. Here, the authors developed complexes between gadolinium and the scaffolding compound DOTA with increased stability, which also lend themselves to radiometal labelling.

    • Lixiong Dai
    • , Chloe M. Jones
    •  & Ga-Lai Law

  • Article
    | Open Access

    White phosphorus and yellow arsenic represent useful elemental sources for synthetic applications, but their poor stabilities make their storage highly challenging. Here, Scheer and colleagues encapsulate P4 and As4 molecules within porous activated carbons and demonstrate their use in subsequent chemical reactions.

    • Andreas E. Seitz
    • , Felix Hippauf
    •  & Manfred Scheer

  • Article
    | Open Access

    Radicals of heavy main-group elements represent important intermediates in chemical synthesis, yet few have been isolated. Here the authors stabilize neutral stibinyl and bismuthinyl radicals using gallium-based ligands, and reduce the former to afford a Ga=Sb double bond-containing complex.

    • Chelladurai Ganesamoorthy
    • , Christoph Helling
    •  & Stephan Schulz

  • Article
    | Open Access

    Single-molecule magnets typically only retain information in the presence of an applied magnetic field and at very low temperatures. Here, Demir, Long and co-workers design N2 3– radical-bridged dilanthanide complexes that exhibit giant coercivities and 100-s magnetic blocking temperatures of up to 20 K.

    • Selvan Demir
    • , Miguel I. Gonzalez
    •  & Jeffrey R. Long

  • Article
    | Open Access

    Metal-carbon σ bonds mark the basis of organometallic chemistry, but the formation of multiple such bonds between single organic and metal entities remains a challenge. Here, the authors report a one-pot aromaticity-driven method to construct osmium-based multidentate complexes containing three metal-carbon σ bonds from multiyn chains.

    • Qingde Zhuo
    • , Jianfeng Lin
    •  & Haiping Xia

  • Article
    | Open Access

    The reactivity of f-block complexes is primarily defined by single-electron oxidations and σ-bond metathesis. Here, Liddle and co-workers provide evidence that a uranium complex can undergo reversible oxidative addition and reductive elimination, demonstrating transition metal-like reactivity within f-block chemistry.

    • Benedict M. Gardner
    • , Christos E. Kefalidis
    •  & Stephen T. Liddle

  • Article
    | Open Access

    The Mannich reaction proceeds by functionalization of C(sp3)-H bonds alpha to carbonyls. Here, the authors suppress the Mannich reactivity of acetophenones in presence of a manganese catalyst and obtain valuable o-aminoalkylacetophenones and isoindolines via C(sp2)-H functionalization with imines.

    • Bingwei Zhou
    • , Yuanyuan Hu
    •  & Congyang Wang

  • Article
    | Open Access

    Converting the normally highly stable amide bond into different functionalities is a challenging task. Here the authors report a nickel-catalysed retro-hydroamidocarbonylation procedure, allowing the conversion of aliphatic amides into alkenes across a range of substrates.

    • Jiefeng Hu
    • , Minyan Wang
    •  & Zhuangzhi Shi

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