Chemical bonding articles within Nature Communications

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  • Article
    | Open Access

    Phosphanorcaradienes can serve as synthons for transient phosphinidene but the synthesis remains challenging. Here, the authors report a synthesis protocol for a phosphanorcaradiene, in which one of the benzene rings is intramolecularly dearomatized through attachment to the phosphorus atom.

    • Yizhen Chen
    • , Peifeng Su
    •  & Gengwen Tan

  • Article
    | Open Access

    7C-10C and 12C-carbolong complexes with planar ligand skeletons containing 7-10 and 12 carbon atoms have been previously reported but 11C-carbolong complexes with a planar carbon-chain ligand are elusive. Here, the authors prepare metallabenzyne-fused metallapentalenes and metallabenzene-fused metallapentalynes, both representing 11C-carbolong complexes with a planar carbon-chain ligand

    • Binbin Xu
    • , Wei Mao
    •  & Haiping Xia

  • Article
    | Open Access

    So far, only homoleptic N2 complexes of silicon have been reported under matrix-isolation conditions including but the activation of more inert nitrogen by silylenes remains challenging. Here the authors report on the activation of dinitrogen by silylenes under cryogenic conditions.

    • Liyan Cai
    • , Bing Xu
    •  & Xuefeng Wang

  • Article
    | Open Access

    Notwithstanding their success as strongly σ-donating and π-accepting ligands, to date no chelating bis[cyclic (alkyl)(amino)carbenes] have been reported. Here the authors describe a chelating, C2-symmetric bis[cyclic (alkyl)(amino)carbene] ligand, as well as its pseudotetrahedral complexes with iron, cobalt, nickel, and zinc dihalides.

    • Braulio M. Puerta Lombardi
    • , Morgan R. Faas
    •  & Roland Roesler

  • 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

    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

    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

    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

    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

    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

    The structure of GeO2 melt has been debated for decades due to several unexplained bands present in the GeO2 melt Raman spectra. Here authors present a promising way to analyse melt structures from Raman spectra and they demonstrate threefold coordinated germanium is formed in the GeO2 melt.

    • Songming Wan
    • , Shujie Zhang
    •  & Jinglin You

  • 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

    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

    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

    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

    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

    The stabilization of low-coordinate boron radicals is challenging, as they tend to form strong chemical bonds. Here the authors report the isolation and structural characterization of a dicoordinate boron radical featuring a π-donating amino and a π-accepting carbene ligand.

    • Yu-Jiang Lin
    • , Wei-Chun Liu
    •  & Ching-Wen Chiu

  • Article
    | Open Access

    The investigation of thermal conductivity is crucial to the success of many modern technologies. Here the authors have reported an unusual glass-like thermal conductivity in a single crystal of layered halide perovskite, Cs3Bi2I6Cl3.

    • Paribesh Acharyya
    • , Tanmoy Ghosh
    •  & Kanishka Biswas

  • Article
    | Open Access

    Photoluminescent gold clusters have unique chemical and physical properties based on their perturbed electronic structures. Here, the authors report the synthesis of carbon-centered Au(I)-Ag(I) clusters with high phosphorescence quantum yields using N-heterocyclic carbene ligands.

    • Zhen Lei
    • , Mizuki Endo
    •  & Mitsuhiko Shionoya

  • Article
    | Open Access

    Several strategies have been developed in recent years for therapeutic induction of ferroptosis in cancer. Here the authors report the design of two hypercarbon-centered gold(I) cluster prodrugs that induce ferroptosis of cancer cells, showing anti-tumor activity in preclinical bladder cancer models.

    • Kui Xiao
    • , Niyuan Zhang
    •  & Liang Zhao

  • Article
    | Open Access

    The reasons for which many low-coordinate complexes exhibit bent geometry, rather than a higher symmetry, are still under debate. Here, the authors use high-pressure crystallography to examine whether low-coordinate f-block molecules become more planar or pyramidal under pressure; which happens is dictated by the dipole moment of the complex and the volume of the planar form.

    • Amy N. Price
    • , Victoria Berryman
    •  & Polly L. Arnold

  • Article
    | Open Access

    The cytochrome P450 enzyme CYP1B1 is overexpressed in a variety of tumors, and is correlated with poor treatment outcomes; thus, it is desirable to develop CYP1B1 inhibitors to restore chemotherapy efficacy. Here the authors describe the creation of light-triggered CYP1B1 inhibitors as “prodrugs”, and achieve >6000-fold improvement in potency upon activation with low-energy (660 nm) light.

    • Dmytro Havrylyuk
    • , Austin C. Hachey
    •  & Edith C. Glazer

  • Article
    | Open Access

    The authors introduce a novel type of chemical bond termed collective bond, which is based on long-range interactions between atoms not considered to be bonded within the Lewis formalisms. Collective bonding occurs among a large family of widely used organometallics.

    • Shahin Sowlati-Hashjin
    • , Vojtěch Šadek
    •  & Cina Foroutan-Nejad

  • Article
    | Open Access

    The number of metal complexes featuring gold-germanium bonds is limited. Here the authors report the preparation of germylene-bridged digold complexes complexes and study their structure, bonding, and reactivity.

    • Liliang Wang
    • , Guorong Zhen
    •  & Zhifang Li

  • Article
    | Open Access

    The formation pathway of shape-anisotropic nanoparticles is difficult to characterize and not well understood. The authors synthesize a prismatic-shaped Au56 nanocluster as possible seed of a prismatic nanoparticle and characterize the structure and ligand bonding motifs, providing insight into the formation and surface protection mechanisms.

    • Yongbo Song
    • , Yingwei Li
    •  & Rongchao Jin

  • Article
    | Open Access

    Conductive and magnetically frustrated solids may enable the development of high-performance molecule-based spintronic devices. Here the authors report a conductive and magnetically frustrated metal–fullerene-bonded framework prepared from a redox-active dinuclear copper complex and lithium ion-encapsulated fullerenes.

    • Yongbing Shen
    • , Mengxing Cui
    •  & Masahiro Yamashita

  • Article
    | Open Access

    High pressure can modify the chemical properties of the elements, giving rise to exotic bonding. Here the authors report the prediction of a nitrogen-rich iodine nitride compound IN6 where the iodine atom has an unusual twelve-fold coordination, stable above 100 GPa.

    • Yan Liu
    • , Rui Wang
    •  & Tian Cui

  • Article
    | Open Access

    The most common oxidation state for lanthanides is +3. Here the authors use photoelectron spectroscopy and theoretical calculations to study half-sandwich complexes where a lanthanide center in the oxidation state +1 is bound to an aromatic wheel-like B82- ligand.

    • Wan-Lu Li
    • , Teng-Teng Chen
    •  & Lai-Sheng Wang

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