European Journal of Inorganic Chemistry

Cover image for Vol. 2013 Issue 22‐23

Special Issue: Small-Molecule Activation by Reactive Metal Complexes (Cluster Issue)

August 2013

Volume 2013, Issue 22-23

Pages 3728–4104

Issue edited by: Connie C. Lu, Karsten Meyer

  1. Cover Picture

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    4. Editorial
    5. Guest Editorial
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    8. Graphical Abstract
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    10. Further Masthead
    11. Microreviews
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      Hydrogen Evolution Catalyzed by Aluminum-Bridged Cobalt Diglyoximate Complexes (Eur. J. Inorg. Chem. 22-23/2013)

      Paul Kelley, Michael W. Day and Theodor Agapie

      Version of Record online: 6 AUG 2013 | DOI: 10.1002/ejic.201390098

      Thumbnail image of graphical abstract

      The cover picture shows the core of the crystal structure of an aluminium-bridged cobalt diglyoximate catalyst for hydrogen evolution. The redox chemistry of such species is dependent on the number of aluminum centers and the nature of the ancillary ligand coordinated to aluminum. Characterization of several cobalt diglyoximato complexes connected by one or two aluminum bridges and their electrocatalytic behavior for proton reduction are discussed in the article by T. Agapie et al. on p. 3840 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

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      Hydrogen Evolution Catalyzed by Aluminum-Bridged Cobalt Diglyoximate Complexes (page 3728)

      Paul Kelley, Michael W. Day and Theodor Agapie

      Version of Record online: 6 AUG 2013 | DOI: 10.1002/ejic.201300806

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      By taking inspiration from nature, research in the Agapie laboratory targets transformations and catalysts that are environmentally friendly, based on synthetic models of active sites of highly efficient enzymes...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 3840 ff.

  3. Editorial

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      Small Molecules – Big Influence! (pages 3729–3730)

      Karen J. Hindson

      Version of Record online: 6 AUG 2013 | DOI: 10.1002/ejic.201300916

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      EurJIC presents you with a superb double issue on a huge variety of topics that cluster around the central topic of small-molecule activation. Guest Editors Karsten Meyer and Connie Lu were excellent hands-on Guest Editors from the start and have compiled an issue with a mix of authors from the well-established pioneers of the field as well as young investigators. EurJIC presents you with a superb double issue on a huge variety of topics that cluster around the central topic of small-molecule activation. Guest Editors Karsten Meyer and Connie Lu were excellent hands-on Guest Editors from the start and have compiled an issue with a mix of authors from the well-established pioneers of the field as well as young investigators.

  4. Guest Editorial

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    1. Small-Molecule Activation by Reactive Metal Complexes (pages 3731–3732)

      Connie C. Lu and Karsten Meyer

      Version of Record online: 6 AUG 2013 | DOI: 10.1002/ejic.201300825

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      An overview of the papers in this cluster issue is presented.

      One of the grand challenges is to develop clean energy for a global green economy. Chemists – as creators and manipulators of molecules – will play a tremendous role towards this future. We will be relied upon to invent and improve catalysts for many useful and needed reactions, of which one of the most important class is the conversion of small molecules of biological and industrial relevance, including H2, H2O, CH4, CO2, N2, and O2...

      Read more by the Guest Editors on p. 3731.

  5. Masthead

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  6. Back Cover

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      Reactions of a Niobium Nitride Complex Prepared from Dinitrogen: Synthesis of Imide and Ureate Complexes and Ammonia Formation (Eur. J. Inorg. Chem. 22-23/2013)

      Fumio Akagi, Shoui Suzuki, Yutaka Ishida, Tsubasa Hatanaka, Tsukasa Matsuo and Hiroyuki Kawaguchi

      Version of Record online: 6 AUG 2013 | DOI: 10.1002/ejic.201390100

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      The back cover picture shows the molecular structure of the niobium ureate complex derived from N2 and CO2. The niobium nitride prepared from N2 activation by niobium hydride was alkylated with methyl iodide to afford the imide complex, which was converted to the ureate complex upon exposure to CO2 in the presence of pyridine. Protonation of the nitride complex yielded ammonia along with niobium chloride, which could be recycled back to the niobium hydride. Details are discussed in the article by H. Kawaguchi et al. on p. 3930 ff.

  7. Graphical Abstract

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  8. News

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  10. Microreviews

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    1. Small-Molecule Activation

      Small-Molecule Activation at Uranium(III) (pages 3753–3770)

      Benedict M. Gardner and Stephen T. Liddle

      Version of Record online: 2 APR 2013 | DOI: 10.1002/ejic.201300111

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      Low-valent, electron-rich UIII complexes have the ability to access a wide range of novel reactivity patterns with small molecules. This microreview focuses on the activation chemistry of trivalent uranium complexes towards the industrially relevant small molecules N2, NO, N3, CO and CO2, outlining the often unexpected chemistry observed for these reactive UIII centres.

    2. Semihydrogenation Catalysis

      Group 5 Imides and Bis(imide)s as Selective Hydrogenation Catalysts (pages 3771–3783)

      Thomas L. Gianetti, Henry S. La Pierre and John Arnold

      Version of Record online: 26 APR 2013 | DOI: 10.1002/ejic.201300202

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      The selective, catalytic semihydrogenation of alkynes by group 5 imido and bis(imido) complexes is presented from synthetic and mechanistic perspectives in the context of previous stoichiometric studies on the d0 metal–ligand multiple-bond activation of strong σ bonds and both stoichiometric and catalytic studies on H2 activation and hydrogenation by d2 group 5 complexes.

    3. Metal–Oxo (Imido) Cores

      Terminal Oxo and Imido Transition-Metal Complexes of Groups 9–11 (pages 3784–3807)

      Kallol Ray, Florian Heims and Florian Felix Pfaff

      Version of Record online: 25 JUN 2013 | DOI: 10.1002/ejic.201300223

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      This review summarizes the properties of group 9–11 metal–oxo and metal–imido complexes with a focus on providing a clear picture of the state of the art as well as insight towards potential future synthetic endeavors.

  11. Short Communications

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    1. Nitrogen Transfer

      A Synthetic Cycle for Nitrogen Atom Transfer Featuring a Diruthenium Nitride Intermediate (pages 3808–3811)

      Amanda R. Corcos, Amanda Kae Musch Long, Ilia A. Guzei and John F. Berry

      Version of Record online: 17 APR 2013 | DOI: 10.1002/ejic.201300180

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      The new Ru2 azido complex [Ru2(chp)4N3] (chp = 2-chloro-6-hydroxypyridinate) reacts with PPh3 under photolytic conditions to form [H2NPPh3]+Cl and [Ru2(chp)4Cl], from which the azide complex can be regenerated.

    2. NO Reactivity

      Copper C-Nitroso Compounds: Activation of Hydroxylamines and NO Reactivity (pages 3812–3816)

      Kamille D. Williams, Allan Jay P. Cardenas, Jennifer D. Oliva and Timothy H. Warren

      Version of Record online: 1 JUL 2013 | DOI: 10.1002/ejic.201300378

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      Copper(I) β-diketiminato and tris(pyrazolyl)borato complexes [CuI] readily bind PhNO to give adducts [[Me2NNF6]Cu(η2-ONPh)] (5) and [iPr2TpCu{κ1-N(O)Ph}] (6) with different nitrosobenzene binding modes. Both products can be obtained upon dismutation of 2 equiv. PhNHOH in the presence of [CuI]. The nitrosobenzene adducts [Cu](ONPh) capture NO to give the copper(II) diazeniumdiolates [CuII](κ2-O2N2Ph).

    3. Group 13 Halides

      Divergent Reactivity of TEMPO with MBr3 (M = B, Al) (pages 3817–3820)

      Ashley M. Wright, Joshua S. Page, Jeremiah J. Scepaniak, Guang Wu and Trevor W. Hayton

      Version of Record online: 17 APR 2013 | DOI: 10.1002/ejic.201300163

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      The outcome of the reaction between TEMPO and MBr3 (M = B, Al) was found to depend on the Lewis acidity of the group 13 element. Addition of TEMPO to AlBr3 results in formation of the 1:1 adduct, AlBr31-TEMPO). In contrast, addition of TEMPO to BBr3 results in TEMPO disproportionation and formation of [TEMPO][BBr4] and (TEMPO)2BBr.

    4. C–H Alumination

      C–H Metalation Reaction of Diarylamine and Carbazole by Alkylaluminum Complexes at the Heteroatom-Bridged Dimeric Aluminum Core (pages 3821–3825)

      Koji Yamamoto, Yu Shibata, Yuki Kashiwa, Ai Kondo, Hayato Tsurugi and Kazushi Mashima

      Version of Record online: 3 APR 2013 | DOI: 10.1002/ejic.201300210

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      Direct metalation reactions of diphenylamine and carbazole were achieved by using amido-bridged dinuclear Al2 complexes. By comparing the inertness of the aryloxido-bridged dinuclear aluminum complexes for the C–H metalation reaction, we found that the Al2N2 core created enough space for the secondary amine substrates to approach the Al–alkyl moiety due to the flexibility of the bridging amido ligand, which allows the Al2N2 core to form both a planar and butterfly shape.

    5. Reductive Nitrile Coupling

      Acetonitrile Coupling at an Electron-Rich Iridium Center Supported by a PCmath imageP Pincer Ligand (pages 3826–3830)

      Richard J. Burford, Warren E. Piers and Masood Parvez

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/ejic.201300152

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      Electron-rich IrI aryl amido complexes undergo heterolytic bond cleavage and one-electron reduction to effect coupling of a coordinated acetonitrile ligand. The dimeric product features a bridging diiminato ligand. The ability to mediate this coupling with a late transition metal attests to the highly donating nature of the PCmath imageP pincer ligand environment.

    6. Redox-Active Ligands

      Redox-Induced Carbon–Carbon Bond Formation by Using Noninnocent Ligands (pages 3831–3835)

      Thomas W. Myers, Gereon M. Yee and Louise A. Berben

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/ejic.201300192

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      Oxidation of (IP)2Al(CH3) (IP = iminopyridine) with TrBPh4 (Tr = trityl) affords the C–C-coupled kinetic product [(IP)(Tr-IP)Al(CH3)][BPh4] in which the trityl radical and the IP radical have undergone C–C bond formation. Oxidation of (IP)2Al(CH3) with TrBArF24 affords the thermodynamic product [(IP)(IP)Al(CH3)][BarF24] {BArF24 = tetrakis[(3,5-trifluoromethyl)phenyl]borate}.

    7. Chalcogenonitrosyl Complexes

      Thionitrosyl- and Selenonitrosyliridium Complexes (pages 3836–3839)

      Markus G. Scheibel, Isabel Klopsch, Hilke Wolf, Peter Stollberg, Dietmar Stalke and Sven Schneider

      Version of Record online: 6 AUG 2013 | DOI: 10.1002/ejic.201377409

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      The nitridoiridium complex [Ir(N){N(CHCHPtBu2)2}]PF6 is oxidized by elemental sulfur and selenium to the corresponding thionitrosyl and selenonitrosyl complexes to give access to a rare example for a full M(NE) (E = none, O, S, Se) series. Bonding is discussed on the basis of crystallographic and spectroscopic characterization.

  12. Full Papers

    1. Top of page
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    1. Hydrogen Evolution

      Hydrogen Evolution Catalyzed by Aluminum-Bridged Cobalt Diglyoximate Complexes (pages 3840–3845)

      Paul Kelley, Michael W. Day and Theodor Agapie

      Version of Record online: 14 MAY 2013 | DOI: 10.1002/ejic.201300309

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      Cobalt diglyoximate complexes connected by aluminum bridges were synthesized. The redox chemistry of these species is dependent on the number of aluminum centers and the nature of the ancillary ligand coordinated to aluminum. Proton reduction to hydrogen was observed and compared to BF2- and proton-bridged analogs.

    2. Water-Oxidation Catalysis

      Incorporation of Hydrogen-Bonding Functionalities into the Second Coordination Sphere of Iron-Based Water-Oxidation Catalysts (pages 3846–3857)

      Wesley A. Hoffert, Michael T. Mock, Aaron M. Appel and Jenny Y. Yang

      Version of Record online: 9 APR 2013 | DOI: 10.1002/ejic.201201499

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      The structural, electrochemical, and catalytic properties of a family of iron-containing homogeneous water oxidation catalysts with pendant heteroatoms are studied. Slightly faster O2 evolution relative to a parent compound is observed when the solvent pH is matched to the pKa of the pendant nitrogen base, which might be attributable to interactions with substrate water.

    3. Non-Heme Iron Complexes

      An Iron(II)[1,3-bis(2′-pyridylimino)isoindoline] Complex as a Catalyst for Substrate Oxidation with H2O2 – Evidence for a Transient Peroxidodiiron(III) Species (pages 3858–3866)

      József S. Pap, Matthew A. Cranswick, É. Balogh-Hergovich, Gábor Baráth, Michel Giorgi, Gregory T. Rohde, József Kaizer, Gábor Speier and Lawrence Que Jr.

      Version of Record online: 7 JUN 2013 | DOI: 10.1002/ejic.201300162

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      A monoiron(II) complex of 1,3-bis(2′-pyridylimino)isoindoline reacts with H2O2 to form a green diiron(III) peroxido intermediate, which may serve as the precursor to the active oxidant in thioanisole and benzyl alcohol oxidation.

    4. Hydrogen Peroxide Disproportionation

      A Robust Mn Catalyst for H2O2 Disproportionation in Aqueous Solution (pages 3867–3873)

      Wei-Tsung Lee, Song Xu, Diane A. Dickie and Jeremy M. Smith

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/ejic.201300184

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      The macrocycle complex [(Py2N2)Mn(H2O)2]2+ catalyses H2O2 disproportionation in aqueous solution, achieving large turnover numbers and operating over a wide pH range. Mechanistic studies implicate a monomeric catalyst for H2O2 disproportionation.

    5. E–H Activation

      Activation of E–H and E–E (E = S, O) Bonds by Heterobimetallic Zr/Co Complexes: Evidence for Both One- and Two-Electron Processes (pages 3874–3882)

      J. Wesley Napoline, Jeremy P. Krogman, Rena Shi, Subramaniam Kuppuswamy, Mark W. Bezpalko, Bruce M. Foxman and Christine M. Thomas

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/ejic.201300122

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      A highly reactive phosphanylamide-supported Zr/Co complex has been shown to react with alcohols, thiols, peroxides, and disulfides by means of a dissociative electron-transfer process occurring at Zr. A range of products are formed depending on the identity of the substrate, including both one- and two-electron oxidized products.

    6. Modeling Sulfite Reductase

      Connecting [4Fe–4S] Clusters and Hemes – Towards Modeling the Active Site of Sulfite Reductase (pages 3883–3890)

      Deidra L. Gerlach, Dimitri Coucouvanis and Nicolai Lehnert

      Version of Record online: 17 JUN 2013 | DOI: 10.1002/ejic.201300308

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      The binding between fluorinated zinc porphyrins and site-differentiated [4Fe–4S] clusters through pyridyl- and imidazolylthiolate bifunctional bridging ligands generates catalytic arrays inspired by the active site of sulfite reductase. The properties of the unique [4Fe–4S] clusters applied here are described, and binding constants are reported for the two components of the resulting macromolecular scaffold.

    7. Dinitrogen Complexes

      Cobalt–Magnesium and Iron–Magnesium Complexes with Weakened Dinitrogen Bridges (pages 3891–3897)

      Thomas R. Dugan, K. Cory MacLeod, William W. Brennessel and Patrick L. Holland

      Version of Record online: 17 JUN 2013 | DOI: 10.1002/ejic.201300187

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      Diketiminate-supported iron and cobalt complexes react with activated magnesium in tetrahydrofuran (THF) to give complexes with M–NN–Mg–NN–M (M = Fe, Co) cores. The Mg ion prefers to bind end-on to N2, which contrasts with the side-on binding of N2 by sodium and potassium ions in previous complexes.

    8. Dinitrogen Activation

      Dinitrogen Activation at Iron and Cobalt Metallalumatranes (pages 3898–3906)

      P. Alex Rudd, Nora Planas, Eckhard Bill, Laura Gagliardi and Connie C. Lu

      Version of Record online: 4 JUL 2013 | DOI: 10.1002/ejic.201300272

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      An alumatrane ligand is used to support electron-rich ferrate(1–) and cobaltate(1–) centers within anionic metallalumatrane complexes. These complexes activate dinitrogen weakly. In the case of ferrate, the bound dinitrogen can be converted into to a disilylhydrazido(2–) ligand.

    9. N–N Activation

      Dinitrogen Borylation with Group 4 Metallocene Complexes (pages 3907–3915)

      Scott P. Semproni and Paul J. Chirik

      Version of Record online: 27 MAR 2013 | DOI: 10.1002/ejic.201300046

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      Use of pinacolborane to borylate a hafnocene complex with a highly activated, side-on bound dinitrogen ligand resulted in N–B and M–H bond formation. Carbonylation of the functionalized hafnocene product triggers N–N cleavage to borylimido and formamidido ligands, thereby expanding the scope of CO-induced N2 bond cleavage.

    10. Nitride Reactivity

      Formation and Reactivity of the Terminal Vanadium Nitride Functionality (pages 3916–3929)

      Ba L. Tran, J. Krzystek, Andrew Ozarowski, Chung-Hsing Chen, Maren Pink, Jonathan A. Karty, Joshua Telser, Karsten Meyer and Daniel J. Mindiola

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/ejic.201300178

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      The transformation of VIII azides to the corresponding VV nitrides was investigated through isotopic labeling crossover experiments, SQUID magnetization, and multifrequency/high-field EPR studies. While Lewis bases inhibit the azide-to-nitride transformation, nitride complexes are formed by a bimetallic mechanism. Stoichiometric Lewis acid and catalytic amount of VII complex also rendered azide-to-nitride formation. However, Lewis bases inhibit formation of nitride product.

    11. Nitride Compounds

      Reactions of a Niobium Nitride Complex Prepared from Dinitrogen: Synthesis of Imide and Ureate Complexes and Ammonia Formation (pages 3930–3936)

      Fumio Akagi, Shoui Suzuki, Yutaka Ishida, Tsubasa Hatanaka, Tsukasa Matsuo and Hiroyuki Kawaguchi

      Version of Record online: 10 MAY 2013 | DOI: 10.1002/ejic.201300172

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      The niobium nitride complex prepared from N2 was protonated to generate NH3, while the reaction with methyl iodide gave the methyl imide complex. Exposure of the imide complex to CO2 gave the ureate complex along with the oxo-bridged dinuclear complex.

    12. Diazene Reduction

      Reduction and Hydrogenation of a Diazene by a (β-Diketiminato)nickel Hydrazide (pages 3937–3942)

      Claudia Köthe, Ramona Metzinger and Christian Limberg

      Version of Record online: 11 APR 2013 | DOI: 10.1002/ejic.201300064

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      A (β-diketiminato)nickel hydrazido(1–) complex has been synthesized that acts as a four-electron reductant towards a diazene: The corresponding hydrazine is formed, as well as a novel trinuclear complex with bridging hydrazido(2–) ligands, which can also be obtained through activation of the diazene at nickel(I) precursors.

    13. Carbene Ligands

      Small-Molecule Activation with Molybdenum(0) Complexes Supported by Mixed Imidazol-2-Ylidene/Phosphanyl Hybrid Ligands – Electronic and Structural Consequences of Substituting a Phosphane by a Carbene Group (pages 3943–3955)

      Christian Gradert, Jan Krahmer, Frank D. Sönnichsen, Christian Näther and Felix Tuczek

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/ejic.201300177

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      Mo carbonyl complexes with mixed N-heterocyclic carbene (NHC)/phosphane ligands and those with pure NHC and phosphane ligands are compared. Whereas the σ-donor strengths of phosphane and carbene groups are comparable, the π-acceptor interactions of the carbene moieties are exactly canceled by π-donor interactions.

    14. Abnormal-Carbene Ligands

      Activating Azides and Alkynes for the Click Reaction with [Cu(aNHC)2I] or [Cu(aNHC)2]+ (aNHC = Triazole-Derived Abnormal Carbenes): Structural Characterization and Catalytic Properties (pages 3956–3965)

      Stephan Hohloch, Damaris Scheiffele and Biprajit Sarkar

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/ejic.201300150

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      Cationic copper(I) complexes containing two triazolylidene carbenes of the abnormal type are shown to be excellent catalysts for the [3+2] cycloaddition reaction between azides and alkynes. A range of azides and a couple of alkynes are activated by these copper(I) complexes towards the catalytic formation of the corresponding substituted 1,2,3-triazoles.

    15. Hydrogen Activation

      Synthesis of Coordinatively Unsaturated Half-Sandwich Iron–Silyl Complexes with an N-Heterocyclic Carbene Ligand and Their Reactions with H2 (pages 3966–3971)

      Tsubasa Hatanaka, Yasuhiro Ohki and Kazuyuki Tatsumi

      Version of Record online: 11 MAR 2013 | DOI: 10.1002/ejic.201300045

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      A half-sandwich, 16-electron iron complex with a cyclometalated N-heterocyclic carbene ligand was found to activate the Si–H bonds of hydrosilanes, thus giving rise to coordinatively unsaturated iron–silyl complexes. The silyl complexes interact with H2 to form 18-electron dihydride complexes.

    16. Nonclassical Hydrogenation Catalysis

      In Situ X-ray Absorption Spectroscopy and Nonclassical Catalytic Hydrogenation with an Iron(II) Catecholate Immobilized on a Porous Organic Polymer (pages 3972–3977)

      Steven J. Kraft, Bo Hu, Guanghui Zhang, Jeffrey T. Miller and Adam S. Hock

      Version of Record online: 12 JUL 2013 | DOI: 10.1002/ejic.201300528

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      We have characterized an iron catecholate catalyst immobilized on a 3-dimensional porous polymer by in situ X-ray absorption spectroscopy. The oxidation state of Fe under a dihydrogen atmosphere is +2, but it readily is oxidized to Fe3+ upon exposure to ambient air. The Fe2+ material in hydrogen at 150 °C catalyzes the hydrogenation of olefins. Potential mechanisms for this nonclassical catalysis are discussed.

    17. Hydrogen Activation

      Isolation and Crystal Structure of the Proposed Low-Valent Active Species in the H2 Activation Catalytic Cycle (pages 3978–3986)

      Daisuke Inoki, Takahiro Matsumoto, Hidetaka Nakai and Seiji Ogo

      Version of Record online: 29 MAY 2013 | DOI: 10.1002/ejic.201300049

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      A two-electron-reduced dinuclear IrII–IrII complex was synthesized by the reaction of a mononuclear IrIII aqua complex by extraction of electrons from H2 in water under ambient conditions.

    18. Early Lanthanide Complexes

      Hydrido and Allyl/Hydrido Complexes of Early Lanthanides Supported by an NNNN-Type Macrocyclic Ligand (pages 3987–3992)

      Daniel Martin, Julian Kleemann, Elise Abinet, Thomas P. Spaniol, Laurent Maron and Jun Okuda

      Version of Record online: 26 APR 2013 | DOI: 10.1002/ejic.201300167

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      Tetranuclear [Ln(Me3TACD)(μ-H)2]4 [Ln = Ce (1-Ce), Pr (2-Pr)] and dinuclear [Ln(Me3TACD)(η3-C3H5)(μ-H)]2 [Ln = Nd (3-Nd), Sm (4-Sm)] have been obtained by treatment of the corresponding bis(allyl) Me3TACD complexes with phenylsilane and were tested as catalysts in the copolymerization of cyclohexene oxide with CO2.

    19. [Fe]-Hydrogenase Mimic

      Electronic Elements Governing the Binding of Small Molecules to a [Fe]-Hydrogenase Mimic (pages 3993–3999)

      Matthew D. Wodrich and Xile Hu

      Version of Record online: 16 APR 2013 | DOI: 10.1002/ejic.201300081

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      The electronic effects that dictate the binding of small molecules to a [Fe]-hydrogenase mimic are examined by DFT computations. Analysis reveals that a ligand's ability to donate electron density to the Fe centre determines the overall reaction free energy.

    20. Carbon Monoxide Activation

      CO Activation by (Diphosphane)platinum(0): Carbonate and Acetone Formation – Experimental and Mechanistic Study (pages 4000–4007)

      Emmanuel Nicolas, Grégory Nocton and Nicolas Mézailles

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/ejic.201300182

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      The easy access at room temperature to a monocarbonyl–Pt0 complex source allows the addition of stoichiometric amounts of MeI and the formation of acetone, while a PtII carbonate complex forms in the presence of O2. Structural insights into the reaction products and calculated mechanisms are reported.

    21. Carbon Dioxide Reduction

      Pyridinediimine Iron Dicarbonyl Complexes with Pendant Lewis Bases and Lewis Acids Located in the Secondary Coordination Sphere (pages 4008–4015)

      Zachary Thammavongsy, Micah E. LeDoux, Andrew G. Breuhaus-Alvarez, Takele Seda, Lev N. Zakharov and John D. Gilbertson

      Version of Record online: 5 JUL 2013 | DOI: 10.1002/ejic.201300376

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      A series of direduced-dicarbonyl iron pyridinediimine complexes containing either pendant Lewis bases or Lewis acids in the secondary coordination sphere were synthesized and examined for the electrochemical release of CO.

    22. Dimeric Copper Complexes

      A Series of Dinuclear Copper Complexes Bridged by Phosphanylbipyridine Ligands: Synthesis, Structural Characterization and Electrochemistry (pages 4016–4023)

      Alyssia M. Lilio, Kyle A. Grice and Clifford P. Kubiak

      Version of Record online: 25 JAN 2013 | DOI: 10.1002/ejic.201201208

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      Three phosphanylbipyridine ligands that react with CuI to form dimeric complexes have been synthesized and structurally characterized. The Cu–Cu distance can be controlled by ligand substitution, and electrochemical studies of the dimers suggest that four sequential 1e reductions of the bipyridine ligands occur. Catalytic behavior is observed under CO2.

    23. Carbon Dioxide Activation

      Kinetic and Thermodynamic Investigations of CO2 Insertion Reactions into Ru–Me and Ru–H Bonds – An Experimental and Computational Study (pages 4024–4031)

      Donald J. Darensbourg, Samuel J. Kyran, Andrew D. Yeung and Ashfaq A. Bengali

      Version of Record online: 7 JUN 2013 | DOI: 10.1002/ejic.201300179

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      Kinetic measurements of CO2 insertion into the Ru–H and Ru–Me bonds of trans-Ru(dmpe)2(X)R [R = H, Me; dmpe = 1,2-bis(dimethylphosphino)ethane] have shown that these processes are sensitive to the electron-donating ability of X, and poorly electron-donating X ligands have a negative impact. Computational studies of reaction barriers and reaction enthalpies support these observations.

    24. Iridium-Catalyzed Hydrogenation

      A Computational Investigation of the Insertion of Carbon Dioxide into Four- and Five-Coordinate Iridium Hydrides (pages 4032–4041)

      Wesley H. Bernskoetter and Nilay Hazari

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/ejic.201300170

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      The insertion of CO2 into iridium hydrides has been proposed as a crucial step in the iridium-catalyzed hydrogenation of CO2. We used DFT to explore the mechanism of CO2 insertion into five-coordinate iridium(III) dihydrides and four-coordinate iridium(I) monohydrides with pincer ligands, and also calculated the catalytic cycle for thermal CO2 hydrogenation starting from an iridium(III) dihydride.

    25. Reactions of Samarium Diiodide

      Preliminary Theoretical Insights into SmI2-Mediated Reactions: Activation of Ketones in THF (pages 4042–4049)

      Christos E Kefalidis, Lionel Perrin and Laurent Maron

      Version of Record online: 7 JUN 2013 | DOI: 10.1002/ejic.201300288

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      SmI2(THF)n as well as its reactivity towards benzophenone have been studied by means of DFT calculations. Preliminary results establish the speciation of SmI2 in THF, quantify the lability of ligands and assess the energetics of reduction of the ketone. We show that [(THF)nI2Sm(μ-OCPh2)]2 is unlikely to be on the pathway of pinacol coupling due its high energy.

    26. Actinides

      Bringing Redox Reactivity to a Redox Inactive Metal Center – E–I (E = C, Si) Bond Cleavage with a Thorium Bis(α-diimine) Complex (pages 4050–4055)

      Agnes Mrutu, Charles L. Barnes, Suzanne C. Bart and Justin R. Walensky

      Version of Record online: 23 MAY 2013 | DOI: 10.1002/ejic.201300390

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      The reactivity of a redox-active thorium(IV) complex with CH3I and Me3SiI is shown to be divergent. This is a rare example of the use of redox-active ligands with the actinides.

    27. Cyclometalation

      Lewis Bases Trigger Intramolecular CH–Bond Activation: (tBu3SiO)2W=NtBu [rlhar2] (tBu3SiO)(κOC-tBu2SiOCMe2CH2)HW=NtBu (pages 4056–4067)

      Michael P. Marshak, Devon C. Rosenfeld, Wesley D. Morris, Peter T. Wolczanski, Emil B. Lobkovsky and Thomas R. Cundari

      Version of Record online: 10 MAY 2013 | DOI: 10.1002/ejic.201300234

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      The symmetry-forbidden cyclometalation of (silox)2W=NtBu (1, silox = OSitBu3) to (silox)(tBuN)W(H)(κO,κC-OSitBu2CMe2CH2) (2) and the oxidative addition of dihydrogen to give (silox)2(tBuN=)WH2 (3) are catalyzed by phosphane bases with cone angles < 160°. Quantum mechanics/molecular mechanics (QM/MM) calculations support the experimental findings and show that Lewis bases promote σ/π mixing.

    28. Cooperative X–H Bond Activation

      Activation of X–H Bonds (X = N, P, O, S) with SCS Pincer Palladium Complexes: A Theoretical Study (pages 4068–4076)

      Emmanuel Nicolas, Blanca Martin-Vaca, Nicolas Mézailles, Didier Bourissou and Laurent Maron

      Version of Record online: 13 JUN 2013 | DOI: 10.1002/ejic.201300320

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      Coordination versus bond activation of several X–H substrates was studied by DFT calculations for SCS pincer palladium complexes featuring methanediide and indenediide backbones.

    29. Copper and Nickel Complexes

      Reactivity of (Dicarboxamide)MII–OH (M = Cu, Ni) Complexes – Reaction with Acetonitrile to Yield MII–Cyanomethides (pages 4077–4084)

      Jacqui Tehranchi, Patrick J. Donoghue, Christopher J. Cramer and William B. Tolman

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/ejic.201300328

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      In a unique conversion, copper(II) and nickel(II) hydroxide complexes supported by a sterically unhindered pyridyl(dicarboxamide) ligand react with CH3CN to yield cyanomethide complexes. Oxidations of the CuII–OH and –CH2CN species are also explored.

    30. Uranium Sandwich Complexes

      The First Example of the Two-Electron Reduction of a Phosphaalkyne – Synthesis and Structural Characterisation of the Diuranium(IV) Pentalene Complex [(U{η5-C5Me5}{η8-C8H4(SiiPr3-1,4)2})2(μ-η21-tBuCP)] (pages 4085–4089)

      Nikolaos Tsoureas, Alexander F. R. Kilpatrick, Owen T. Summerscales, John F. Nixon, F. Geoffrey N. Cloke and Peter B Hitchcock

      Version of Record online: 7 MAY 2013 | DOI: 10.1002/ejic.201300256

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      The two-electron reduction of the phosphaalkyne tBuC≡P by the UIII mixed-sandwich complex [U(η5-C5Me5){η8-C8H4(SiiPr3)2}] yields the diuranium(IV) product [(U{η5-C5Me5}{η8-C8H4(SiiPr3)2})2(μ-tBuCP)], which contains a μ-η21-ligated phosphaalkene dianion.

    31. La and Lu Polyphosphide Complexes

      P4 Activation by Lanthanum and Lutetium Naphthalene Complexes Supported by a Ferrocene Diamide Ligand (pages 4090–4096)

      Wenliang Huang and Paula L. Diaconescu

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/ejic.201300225

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      Zintl-type P73– complexes were synthesized from direct activation of P4 by lanthanum and lutetium naphthalene complexes. The P73– complexes showed fluxional behavior dependent on the rare-earth metal.

    32. Half-Sandwich Complexes

      Synthesis of [Cp′Fe(η3-BH4)] and Its Conversion to [Cp′FeBH2]3 (pages 4097–4104)

      Miyuki Maekawa, Constantin G. Daniliuc, Peter G. Jones, Johannes Hohenberger, Jörg Sutter, Karsten Meyer and Marc D. Walter

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/ejic.201300168

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      Diamagnetic [Cp′Fe(η3-BH4)] can be converts cleanly to the trimeric [Cp′FeBH2]3 and H2 at ambient temperature. DFT computations were used to rationalize the bonding in these molecules.

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