Organometallic chemistry articles within Nature Communications

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  • Article
    | Open Access

    Chemical reduction of alkali cations to their metals is extremely challenging. Here, the authors synthesized a series of redox-active borate anions stabilized by bipyridine ligands which can reduce lithium ions generating elemental lithium metal and borate radicals.

    • Haokun Li
    • , Jiachen Yao
    •  & Zhenpin Lu

  • Article
    | Open Access

    Many alkyl fluorides are readily available, but the synthetic applications trail behind the widely accepted utility of other halides. Here, the authors report a practical Csp3-F bond functionalization method that expands the currently restricted synthetic space of unactivated C(sp3)-F bonds, but also uses benzylic, propargylic and acyl fluorides.

    • D. Lucas Kane
    • , Bryan C. Figula
    •  & Christian Wolf

  • Article
    | Open Access

    Extracting rare earth elements (REEs) from wastewater is essential for the growth of an eco-friendly sustainable economy but separating individual rare earth elements remains challenging. Here, the authors report a REE nanotrap that features dense uncoordinated carboxyl groups and triazole N atoms in a two-fold interpenetrated metalorganic framework which is highly responsive to the size variation of rareearth ions.

    • Qing-Hua Hu
    • , An-Min Song
    •  & Jian-Ding Qiu

  • Article
    | Open Access

    Metal-metal interfaces hold promise as contacting moieties for single-molecule devices with tunable functionality, yet the direct bonding has remained a challenge. Here, Lee et al. report the formation of Fe-Au bond without chemical ligand support in ferrocene-based molecular junctions.

    • Woojung Lee
    • , Liang Li
    •  & Latha Venkataraman

  • Article
    | Open Access

    Coordination-induced bond weakening (CIBW) by redox-active metals is used to weaken bonds in water and ammonia to facilitate proton-coupled electron transfer but achieving CIBW using aluminium as abundant metal is challenging. Here, the authors report a system that uses aluminum with a redox non-innocent ligand to achieve CIBW of O-H and N-H bonds.

    • Soumen Sinhababu
    • , Roushan Prakash Singh
    •  & Neal P. Mankad

  • Article
    | Open Access

    Ultrasmall metallic clusters receive great attention for atom-efficient catalysts. Here a metallic cluster–organic framework is synthesized and characterized; authors demonstrate its stability and catalytic proficiency, paving the way for molecular-scale metal nanoparticle interlocking.

    • Xiyue Liu
    • , James N. McPherson
    •  & Kasper S. Pedersen

  • Article
    | Open Access

    Molecular passivation is promising for improving the performance and operation stability of perovskite solar cells. Here, authors employ piperazine dihydriodide to strengthen adhesion to MA-free perovskite via −NH2I and Mulliken charge distribution, realizing charge-regulated molecular passivation.

    • Dhruba B. Khadka
    • , Yasuhiro Shirai
    •  & Kenjiro Miyano

  • Article
    | Open Access

    Exploration of molybdenum complexes as homogeneous hydrogenation catalysts has garnered significant attention, but hydrogenation of unactivated olefins under mild conditions are scarce. Here, the authors report the synthesis of a cationic Mo(II) complex, which exhibits intriguing reactivity toward C2H2 and H2 under ambient pressure.

    • Minghui Xue
    • , Zhiqiang Peng
    •  & Wenguang Wang

  • Article
    | Open Access

    The synthesis of molecular knots remains challenging. Here, the authors report the synthesis of a chiral molecular trefoil metallaknot by self-assembly which contains only 54 atoms in the backbone.

    • Zhiwen Li
    • , Jingjing Zhang
    •  & Richard J. Puddephatt

  • Article
    | Open Access

    Trimetallic carbido clusterfullerenes (CCFs) represent the simplest metal carbido complexes with the ligands being only carbon atoms, but the formation prerequisite is unclear. Herein, the authors report the syntheses of three novel vanadium(V)-based CCFs featuring high vanadium valence state and propose a supplemental Octet Rule

    • Runnan Guan
    • , Jing Huang
    •  & Su-Yuan Xie

  • Article
    | Open Access

    Shortening the inter-spin distance is an effective way to enhance magnetic coupling. However, it is typically challenging to change the inter-ion distance in most magnetic systems. Here, Huang et al present a strategy for enhancing magnetic interactions, by confining a molecular magnetic system inside a carbon fullerene cage, leading to enhanced magnetic properties.

    • Chenli Huang
    • , Rong Sun
    •  & Song Gao

  • Article
    | Open Access

    Here the authors demonstate that counter to expectation provided by the relevant standard reduction potentials, a chloroberyllate, [{SiNDipp}BeClLi]2, reacts with the group 1 elements (M = Na, K, Rb, Cs) to provide the respective heavier alkali metal analogues, [{SiNDipp}BeClM]2.

    • Kyle G. Pearce
    • , Han-Ying Liu
    •  & Michael S. Hill

  • Article
    | Open Access

    While heat modification is ubiquitous in biologic systems, it remains a significant challenge in artificial systems. Here the authors demonstrate thermal regulation of conversion between different rigid macrocycle atropisomers and related self-assemblies.

    • Jiaqi Liang
    • , Shuai Lu
    •  & Han-Yuan Gong

  • Article
    | Open Access

    Despite the rich coordination chemistry, hydroxylamines are rarely used as ligands for transition metal coordination compounds. Here the authors designed macrocyclic poly-N-hydroxylamines that form complexes containing a d-metal ion and coordinate by up to six hydroxylamine fragments.

    • Vladislav K. Lesnikov
    • , Ivan S. Golovanov
    •  & Alexey Yu. Sukhorukov

  • Article
    | Open Access

    Three-component dehydrogenative coupling reactions represent important and practical methodologies for forging new C–N bonds and C–C bonds but achieving all-in-one dehydrogenative coupling functionalization by a single catalytic system remains a great challenge. Here, the authors develop a rigid flexible-coupled copper using a tridentate N-heterocyclic carbene ligand to achieve dehydrogenative coupling using a single catalyst system.

    • Teng Jia
    • , Yi-Xin Li
    •  & Shuang-Quan Zang

  • Article
    | Open Access

    Deep-blue emitters and corresponding light-emitting devices are still in the progress to meet industrial standards. Here, the authors report catalytic interconversion of isomeric iridium(III) complexes and achieve true-blue emission and operational half-lifetime of over 10,000 h for tandem devices.

    • Jie Yan
    • , Dong-Ying Zhou
    •  & Yun Chi

  • Article
    | Open Access

    Enzymatic degradation of pollutants under mild conditions is promising for efficient degradation of environmental contaminants under facile operation conditions, but natural enzymes tend to lose enzymatic activity in environmental application scenarios. Here, the authors report a metal-organic frameworks-based artificial enzyme system to achieve high hydrolytic activity under mild conditions.

    • Xin Yuan
    • , Xiaoling Wu
    •  & Wenyong Lou

  • Article
    | Open Access

    Azulene-based conjugated systems are of great interests due to their unusual structures and photophysical properties but incorporation of a transition metal into azulene skeleton presents remains elusive. Here, the authors describe an efficient [5 + 2] annulation reaction for the rapid construction of a metalla-dual-azulene.

    • Hai-Cheng Liu
    • , Kaidong Ruan
    •  & Haiping Xia

  • Article
    | Open Access

    The introduction of metal sites into polyoxometalates is key for tuning their structure and reactivity but the complex mechanisms which govern metal functionalization of polyoxometalates are still poorly understood. Here, the authors report a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di- metal-functionalization of a prototype molecular vanadium oxide cluster

    • Stefan Repp
    • , Moritz Remmers
    •  & Carsten Streb

  • Article
    | Open Access

    The synthesis and isolation of d-block metallocenes with more than 18-electron is challenging since metal–carbon bonds become weaker with increasing deviation from the 18-electron configuration. Here the authors report a formal 21-electron cobaltocene derivative by coordination of a two-electron donor to a 19-electron cobaltocene derivative while maintaining the cobalt-carbon bonds.

    • Satoshi Takebayashi
    • , Jama Ariai
    •  & Kazunobu Sato

  • Article
    | Open Access

    Metalloligands provide a potent strategy for manipulating the surface metal arrangements of metal nanoclusters (NCs), but their synthesis and subsequent installation onto metal NCs remains a significant challenge. Here, the authors demonstrate the synthesis of two atomically precise silver NCs by controlling reaction temperature and demonstrate thermal induced structure transformation between the clusters during a temperature-dependent assembly process.

    • Zhi Wang
    • , Yan-Jie Zhu
    •  & Di Sun

  • Article
    | Open Access

    Classical metalation reactions in organic synthesis typically involve metal-halogen exchange. Here, the authors introduce a metal-carbon exchange strategy that enables the skeletal editing of biologically relevant lactams by a Ni(0) compound.

    • Hongyu Zhong
    • , Dominic T. Egger
    •  & Bill Morandi

  • Article
    | Open Access

    Understanding the intermetallic synergy and the structure-performances relationships of catalysts remains challenging. Here, the authors demonstrate a relationship between both the rates, selectivity and the s-block metal acidity in a series of heterodinuclear catalysts based on Co(III) in combination with alkali and alkaline earth metals for three different polymerization reactios.

    • Francesca Fiorentini
    • , Wilfred T. Diment
    •  & Charlotte K. Williams

  • Article
    | Open Access

    Understanding and exploiting the redox properties of uranium is of great importance but stabilizing both low and high valent uranium ions in a preserved ligand environment remains challenging. Here, the authors report the synthesis and characterisation of a series of uranium(II–VI) complexes supported by a tripodal tris(amido)arene ligand.

    • Chong Deng
    • , Jiefeng Liang
    •  & Wenliang Huang

  • Article
    | Open Access

    Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Here, the authors report an on-cycle mechanism for CoCl2bpy2 catalyzed Negishi-type cross-coupling describing a full catalytic cycle for this reaction using multiple spectroscopic studies.

    • Xu Luo
    • , Dali Yang
    •  & Aiwen Lei

  • Article
    | Open Access

    CS2 promises easy access to degradable sulfur-rich polymers, but ring-opening copolymerisation using CS2 is challenging due to low linkage selectivity and small-molecule by-products. Here, the authors report a cooperative Cr(III)/K catalyst which selectively delivers poly(dithiocarbonates) from CS2 and oxetanes.

    • Christoph Fornacon-Wood
    • , Bhargav R. Manjunatha
    •  & Alex J. Plajer

  • Article
    | Open Access

    Chiral coinage metal clusters show promise for use in emerging circularly polarized light-emitting materials and diodes but research on efficient circularly polarized organic light-emitting diodes (CP-OLEDs) with enantiopure metal clusters remains elusive. Herein, the authors design a multidentate chiral N-heterocyclic carbene (NHC) ligand which is used in the synthesis of enantiopure Au(I)-Cu(I) clusters with exceptional stability and demonstrate application of these clusters in the fabrication of CP-OLEDs

    • Xiao-Hong Ma
    • , Jing Li
    •  & Shuang-Quan Zang

  • Article
    | Open Access

    Despite the distinct electronic properties of the wide variety Cm3+ compounds that have been prepared to date, no singlecrystal structural characterization of a complex containing a Cm−C bond has been reported. Here the authors report the synthesis of a Cm complex bearing trimethylsilylcyclopentadienyl and 4,4’-bipyridine ligands with a low energy emission and identify the 4,4’-bipyridine ligand as the primary quenching agent.

    • Brian N. Long
    • , María J. Beltrán-Leíva
    •  & Thomas E. Albrecht-Schönzart

  • Article
    | Open Access

    Coordination of benzene by a tungsten complex can minimize the formation of oligomeric aromatic products in Friedel-Crafts Arylation. Here the authors show that coordinating benzene to tungsten through two carbons (dihapto-coordination) enables a rarely observed double protonation of the bound benzene, allowing its subsequent coupling to a second arene without the need of a precious metal or Lewis acid catalyst.

    • Justin T. Weatherford-Pratt
    • , Jacob A. Smith
    •  & W. Dean Harman

  • Article
    | Open Access

    Tetrylones show unique electronic properties and display potantial as soluble molecular allotropes, but until now, the chemistry of Tetrylone homologs remains underexplored. Here, the authors describe the synthesis of a family of antimony(I) and bismuth(I) cations supported by a bis silylene ligand and explore their reactivity.

    • Xuyang Wang
    • , Binglin Lei
    •  & Zhenbo Mo

  • Article
    | Open Access

    Rare-earth and actinide complexes are critical for a wealth of clean-energy applications but Three dimensional (3D) structural generation and prediction for these organometallic systems remains challenging. Here, the authors propose a high-throughput in-silico synthesis code for s-, p-, d-, and f-block mononuclear organometallic complexes.

    • Michael G. Taylor
    • , Daniel J. Burrill
    •  & Ping Yang

  • Article
    | Open Access

    Oxidative coupling of CO is a straightforward but currently underdeveloped economically benign synthetic route to target α-diketones. Here, the authors synthesize a rare coplanar dinuclear hydroxycarbonylcobalt(III) complex and demonstrate that the Co – carboxylate bonds can be easily cleaved leading to the formation of oxalic acid.

    • Yingzhuang Xu
    • , Songyi Li
    •  & Huayi Fang

  • Article
    | Open Access

    Converting low-cost inorganic chemicals into value-added organic chemicals is a longstanding goal in chemistry. Here the authors describe a silver-catalysed chemoselective carbene N−H insertion reaction, providing access to primary amines from aqueous ammonia and diazo compounds.

    • Zhaohong Liu
    • , Yong Yang
    •  & Xihe Bi

  • Article
    | Open Access

    2D and 3D conductive MOFs have performed well in the fields of energy and catalysis. Here, authors synthesise a 1D conductive MOF in which DDA ligands are connected by double Cu ions, forming nanoribbon layers with π-d conjugated nanoribbon planes and out-of-plane π-π stacking, which facilitates charge transport along two dimensions.

    • Shengcong Shang
    • , Changsheng Du
    •  & Jianyi Chen

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