European Journal of Inorganic Chemistry

Cover image for Vol. 2012 Issue 3

Special Issue: Coopertive & Redox Non-Innocent Ligands in Directing Organometallic Reactivity (Cluster Issue)

January 2012

Volume 2012, Issue 3

Pages 340–580

Issue edited by: Bas de Bruin

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Essay
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Microreviews
    9. Short Communications
    10. Full Papers
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      Cooperative Catalysis with First-Row Late Transition Metals (Eur. J. Inorg. Chem. 3/2012)

      Jarl Ivar van der Vlugt

      Article first published online: 16 JAN 2012 | DOI: 10.1002/ejic.201290000

  2. Editorial

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Essay
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Microreviews
    9. Short Communications
    10. Full Papers
    1. You have free access to this content
  3. Essay

    1. Top of page
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    3. Editorial
    4. Essay
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    6. Graphical Abstract
    7. News
    8. Microreviews
    9. Short Communications
    10. Full Papers
    1. Scope of Non-Innocent Ligands

      The Shrinking World of Innocent Ligands: Conventionaland Non-Conventional Redox-Active Ligands (pages 343–348)

      Wolfgang Kaim

      Article first published online: 5 JAN 2012 | DOI: 10.1002/ejic.201101359

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      Evidence for non-innocent ligand behavior is being found for an increasing number of coordination compounds, including those with seemingly unassuming ligands. The recognition of such situations can be exploited for supporting attractive material properties and for understanding and developing chemical reactivity.

  4. Back Cover

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Essay
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Microreviews
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    10. Full Papers
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      Synthesis, Structures, and Transfer Hydrogenation Catalysis of Bifunctional Iridium Complexes Bearing a C–N Chelate Oxime Ligand (Eur. J. Inorg. Chem. 3/2012)

      Megumi Watanabe, Yohei Kashiwame, Shigeki Kuwata and Takao Ikariya

      Article first published online: 16 JAN 2012 | DOI: 10.1002/ejic.201290002

  5. Graphical Abstract

    1. Top of page
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    3. Editorial
    4. Essay
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    6. Graphical Abstract
    7. News
    8. Microreviews
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    1. Graphical Abstract: Eur. J. Inorg. Chem. 3/2012 (pages 350–356)

      Article first published online: 16 JAN 2012 | DOI: 10.1002/ejic.201290003

  6. News

    1. Top of page
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    3. Editorial
    4. Essay
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    6. Graphical Abstract
    7. News
    8. Microreviews
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    10. Full Papers
  7. Microreviews

    1. Top of page
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    3. Editorial
    4. Essay
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    6. Graphical Abstract
    7. News
    8. Microreviews
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    1. Cooperative Catalysis

      Cooperative Catalysis with First-Row Late Transition Metals (pages 363–375)

      Jarl Ivar van der Vlugt

      Article first published online: 29 SEP 2011 | DOI: 10.1002/ejic.201100752

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      A helping hand. This microreview describesrecent developments and opportunities in the rapidly expanding field of bioinspired first-row late transition metal catalysis with cooperative ligand systems. Particular emphasis is placed on hemilabile, redox-noninnocent and adaptive ligand scaffolds and on particular bimetallic strategies.

    2. Iron Catalysis

      Non-Innocent Ligands: New Opportunities in Iron Catalysis (pages 376–389)

      Sébastien Blanchard, Etienne Derat, Marine Desage-El Murr, Louis Fensterbank, Max Malacria and Virginie Mouriès-Mansuy

      Article first published online: 15 DEC 2011 | DOI: 10.1002/ejic.201100985

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      The ability of non-innocent ligands (NILs) to act as a storage/supply unit of electrons promotes one- or two-electron transfers, allowing iron catalysts to perform reactions that were previously restricted to catalysts based on noble metals. Progress in this promising area of research is reviewed with special emphasis on DFT calculations and analysis of spectroscopic data.

    3. Transition-Metal Alkynyl Complexes

      Ligand Redox Non-Innocence in Transition-Metal σ-Alkynyl and Related Complexes (pages 390–411)

      Phil A. Schauer and Paul J. Low

      Article first published online: 13 DEC 2011 | DOI: 10.1002/ejic.201100995

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      Many transition-metal σ-alkynyl complexes are redox-active, undergoing facile oxidation (reduction) at moderate potentials to generate radical cations (anions). This review summarises the diverse chemical behaviour of metal-supported σ-alkynyl radicals, which can often be rationalised in terms of the distribution of electron-spin density over the metal alkynyl scaffold.

    4. Cooperative Pincer Ligands

      Cooperative Aliphatic PNP Amido Pincer Ligands – Versatile Building Blocks for Coordination Chemistry and Catalysis (pages 412–429)

      Sven Schneider, Jenni Meiners and Bjorn Askevold

      Article first published online: 22 NOV 2011 | DOI: 10.1002/ejic.201100880

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      Aliphatic PNP pincer ligands, HN(CH2CH2PR2)2, and ligands derived from them by backbone functionalization, are versatile chelating ligands for metal–ligand cooperative small molecule activation and catalysis. This microreview covers the recent work with these ligands and provides a comprehensive comparison with related pincer systems.

    5. Asymmetric Cyclopropanation

      Ligand Effect on Cobalt(II)-Catalyzed Asymmetric Cyclopropanation with Diazosulfones – Approaching High Stereoselectivity through Modular Design of D2-Symmetric Chiral Porphyrins (pages 430–434)

      Shifa Zhu, Xin Cui and X. Peter Zhang

      Article first published online: 23 DEC 2011 | DOI: 10.1002/ejic.201101023

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      Systematic studies of the ligand effect of CoII complexes of D2-symmetric chiral porphyrins on catalytic asymmetric cyclopropanation with diazosulfones are reviewed. Ligand structures have significantinfluence on both the reactivity and enantioselectivity of the reaction. Catalysts with rigidity have been shown to have high asymmetric induction.

    6. Redox-Active Ligands

      Systematics and Future Projections Concerning Redox-Noninnocent Amide/Imine Ligands (pages 435–443)

      Kenneth G. Caulton

      Article first published online: 14 NOV 2011 | DOI: 10.1002/ejic.201100623

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      Core features of redox-active ligands are analysed and generalized.

    7. Metal–Ligand Electron Transfer

      Metal–Ligand Electron Transfer in 4d and 5d Group 9 Transition Metal Complexes with Pyridine, Diimine Ligands (pages 444–462)

      Daniel Sieh, Mandy Schlimm, Lars Andernach, Friedrich Angersbach, Stefan Nückel, Julia Schöffel, Nevena Šušnjar and Peter Burger

      Article first published online: 5 JAN 2012 | DOI: 10.1002/ejic.201101072

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      The syntheses, X-ray crystal structures, and spectroscopic data for rhodium and iridium pyridine, diimine (PDI) complexes (PDI)Rh,Ir–Ln0,1+ (n = 1–3) are reported for a large variety of ligands L and different coordination numbers (CN = 4–6). The extent of metal–ligand electron transfer in these diamagnetic complexes was evaluated by experimental and theoretical methods.

  8. Short Communications

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Essay
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Microreviews
    9. Short Communications
    10. Full Papers
    1. Redox-Active Ligands

      Unexpected Formation of a Cobalt(III) Phenoxazinylate Electron Reservoir (pages 463–466)

      Frank D. Lesh, Richard L. Lord, Mary Jane Heeg, H. Bernhard Schlegel and Cláudio N. Verani

      Article first published online: 20 DEC 2011 | DOI: 10.1002/ejic.201101352

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      An unexpected aerobic cyclization of the popular redox active N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine ligand occurs in the presence of a cobalt(II) salt to form a new mixed phenolate/phenoxazinylate radical species. Experimental and computational studies elucidate the properties of the resultant bisligated cobalt(III) complex that traverses redox levels from 2+ to 3–.

    2. Electron and Proton Reservoirs

      A Redox-Active Ligand as a Reservoir for Protons and Electrons: O2 Reduction at Zirconium(IV) (pages 467–470)

      Feng Lu, Ryan A. Zarkesh and Alan F. Heyduk

      Article first published online: 10 OCT 2011 | DOI: 10.1002/ejic.201100798

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      The redox-active [ONO] ligand platform coordinates zirconium(IV) to form(ONOcat)ZrCl(THF)2 (1) and (ONHO)ZrCl2(THF) (2). In 2, the ligand retains one proton in addition to its redox-active pair of electrons. Exposure of 2 to O2 results in a four-electron, two-proton reaction to form [(ONOq)ZrCl2(μ-OH)]2 (3). This reaction occurs because the ligand platform serves as a reservoir for both electrons and protons in small-molecule activation reactions.

    3. Spectroelectrochemistry

      Electrochemical Reductive Deprotonation of an Imidazole Ligand in a Bipyridine Tricarbonyl Rhenium(I) Complex (pages 471–474)

      Qiang Zeng, Mahdi Messaoudani, Antonín Vlček Jr. and František Hartl

      Article first published online: 23 NOV 2011 | DOI: 10.1002/ejic.201101100

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      The first example of electrochemical reductive conversion of coordinated imidazole (imH) to the terminal 3-imidazolato (3-im) ligand is reported for fac-[ReI(imH)(CO)3(bpy)]+ (bpy = 2,2′-bipyridine). Its cathodic conversion to fac-[ReI(3-im)(CO)3(bpy)] was studied by variable-temperature UV/Vis/NIR–IR spectroelectrochemistry in an OTTLE cell.

    4. Oxidation of Thiyl Radicals

      Alkyne Addition to a Metal-Stabilized Thiyl Radical: Carbon–Sulfur Bond Formation between 1-Octyne and [Ru(SP)3]+ (pages 475–478)

      Kagna Ouch, Mark S. Mashuta and Craig A. Grapperhaus

      Article first published online: 1 DEC 2011 | DOI: 10.1002/ejic.201101016

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      The addition of 1-octyne to an electrophilic metal-stabilized thiyl radical complex has been induced through chemical and electrochemical oxidation. The alkyne adds irreversibly across the cis-sulfur sites of the metal-thiolate precursor to yield an S-alkylated dithiolene product complex.

    5. Electronic Structure

      A Reduced (β-Diketiminato)iron Complex with End-On and Side-On Nitriles: Strong Backbonding or Ligand Non-Innocence? (pages 479–483)

      Ryan E. Cowley, Gemma J. Christian, William W. Brennessel, Frank Neese and Patrick L. Holland

      Article first published online: 10 OCT 2011 | DOI: 10.1002/ejic.201100787

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      In the S = 3/2 molecule LMeFe(NCtBu)2, the side-on nitrile ligand has N–C–C bending and N–C weakening that suggests partial reduction of the nitrile group. Even though the molecule has three unpaired spins, the interaction between the iron atom and the nitrile ligand is two-electron backbonding rather than redox non-innocence.

  9. Full Papers

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Essay
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Microreviews
    9. Short Communications
    10. Full Papers
    1. Cobalt(II)–Porphyrin Catalysis

      Electronic Effects of Ligands on the Cobalt(II)–Porphyrin-Catalyzed Direct C–H Arylation of Benzene (pages 485–489)

      Tek Long Chan, Ching Tat To, Bei-Sih Liao, Shiuh-Tzung Liu and Kin Shing Chan

      Article first published online: 10 NOV 2011 | DOI: 10.1002/ejic.201100780

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      The electronic effects of porphyrin ligands on the cobalt(II)–porphyrin-catalyzed direct C–H arylation were studied. The reaction rates were found to be dependent on the electronic richness of the porphyrin ligands. Additional axial ligands did not aid the rate-determining abstraction of theiodine atom.

    2. Protons and Noninnocence

      Protonation-Enhanced Lewis Acidity of Iridium Complexes Containing Noninnocent Amidophenolates (pages 490–495)

      Mark R. Ringenberg and Thomas B. Rauchfuss

      Article first published online: 24 NOV 2011 | DOI: 10.1002/ejic.201101011

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      Not just redox: Noninnocent ligands exhibit rich acid–base behavior. Protonation of noninnocent anilidophenolates induces the binding of Lewis bases (CO, PR3, MeCN).Bulky Lewis bases stabilize O-protonation, whereas smaller bases give N-protonated products.

    3. P-Chirogenic Tautomers

      Supramolecular Hydrogen-Bonding Tautomeric Sulfonamido–Phosphinamides: A Perfect P-Chirogenic Memory (pages 496–503)

      Frederic W. Patureau, Maxime A. Siegler, Anthony L. Spek, Albertus J. Sandee, Sylvain Jugé, Sarwar Aziz, Albrecht Berkessel and Joost N. H. Reek

      Article first published online: 28 SEP 2011 | DOI: 10.1002/ejic.201100811

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      Supramolecular hydrogen-bonding sulfonamido–phosphinamides exist as a mixture of tautomers (PIII/PV) in slow equilibrium on the NMR spectroscopic timescale(METAMORPhos). The tautomeric process retains the configuration at the P centre, even in protic solvents. Their resolution allowed up to 99 % ee.

    4. Bifunctional Catalysts

      Synthesis, Structures, and Transfer Hydrogenation Catalysis of Bifunctional Iridium Complexes Bearing a C–N Chelate Oxime Ligand (pages 504–511)

      Megumi Watanabe, Yohei Kashiwame, Shigeki Kuwata and Takao Ikariya

      Article first published online: 10 OCT 2011 | DOI: 10.1002/ejic.201100800

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      A series of organometallic oxime complexes featuring a β-protic OH group have been synthesized. The hydrido-bridgedoxime–oximato complex (pictured) dissociates into two mononuclear species, which are interconvertible through reactions with hydrogen donors and acceptors. Owing to the metal–ligand cooperation, catalytic transfer hydrogenation of ketones with 2-propanol has been achieved.

    5. Multifaceted Reversible Isomerism

      Snapshots of a Reversible Metal–Ligand Two-Electron Transfer Step Involving Compounds Related by Multiple Types of Isomerism (pages 512–519)

      Cristina Tejel, Laura Asensio, M. Pilar del Río, Bas de Bruin, José A. López and Miguel A. Ciriano

      Article first published online: 10 NOV 2011 | DOI: 10.1002/ejic.201100868

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      Four different types of isomerism are involved in the reversible conversion of two isolated isomeric species of the heterodinuclear complex [(cod)Rh(bpa – 2H)Ir(cod)], which contains a redox noninnocent 2-iminopyridine-type ligand. Enthalpy stabilizes the Rh–I{(bpa – 2H)0} isomer (left), whereas entropy is the driving force to generate the RhI{(bpa – 2H)2–} isomer (right).

    6. Organochromium Complexes

      Organochromium Complexes Bearing Noninnocent Diimine Ligands (pages 520–529)

      Kevin A. Kreisel, Glenn P. A. Yap and Klaus H. Theopold

      Article first published online: 27 SEP 2011 | DOI: 10.1002/ejic.201100803

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      A series of organochromium complexes bearing α-diimine ligands has been prepared. The compounds contain diimine ligands in the neutral, singly, and doubly reduced states. All the complexes resist alkyl migration to the diimine backbone, except for a cationic alkyl-CrII species that features a neutral diimine ligand. A C=N insertion mechanism followed by a hydride shift is proposed.

    7. Metal–Alkyl Homolysis

      Radical Chemistry of Iminepyridine Ligands (pages 530–534)

      Peter H. M. Budzelaar

      Article first published online: 29 SEP 2011 | DOI: 10.1002/ejic.201100698

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      Ligands containing at least two imine or pyridine ligands in conjugation reduce the energy required for metal–alkyl homolysis dramatically; ligand alkylation reactions are best explained via free alkyl radicals.

    8. Manganese Compounds

      Synthesis and Electronic Structure of Reduced Bis(imino)pyridine Manganese Compounds (pages 535–545)

      Sarah K. Russell, Amanda C. Bowman, Emil Lobkovsky, Karl Wieghardt and Paul J. Chirik

      Article first published online: 5 OCT 2011 | DOI: 10.1002/ejic.201100569

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      The chemistry of reduced aryl-substituted bis(imino)pyridine manganese complexes has been explored with the goal of elucidating the role of the redox-active chelate. The bis(THF) derivative [(iPrPDI)Mn(THF)2] is a high-spin MnII complex antiferromagnetically coupled to a bis(imino)pyridine diradical, while the related dicarbonyl complex is a low-spin MnI, d6 derivative with a ligand-based SOMO.

    9. Ruthenium Hydride Complexes

      Ruthenium Hydride Complexes with Zwitterionic Quinonoid Ligands – Isomer Separation, Structural Properties, Electrochemistry, and Catalysis (pages 546–553)

      Stephan Hohloch, Pierre Braunstein and Biprajit Sarkar

      Article first published online: 13 DEC 2011 | DOI: 10.1002/ejic.201101091

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      Ruthenium hydride complexes derived from zwitterionic quinonoid ligands have been synthesized, and their isomers have been separated and structurally characterized. Cyclic voltammetry of the complexes showed the redox noninnocent nature of the quinonoid ligands. One of the complexes showed good activity as a catalyst for the transfer hydrogenation of acetophenone.

    10. Redox-Active Ligand Catalysis

      Aerobic Alcohol Oxidations Catalyzed by Oxorhenium Complexes Containing Redox-Active Ligands (pages 554–561)

      Cameron A. Lippert, Korbinian Riener and Jake D. Soper

      Article first published online: 24 NOV 2011 | DOI: 10.1002/ejic.201101044

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      The capacity of oxorhenium(V) anions with redox-active catecholate ligands to homolyze O2 and generate dioxorhenium(VII) products is utilized for oxidase-type alcohol oxidations. Formation of the active oxidant requires both the dioxo and monooxo species. The scope and limitations of this redox-active ligand-mediated catalysis are discussed.

    11. C–H Amination

      Dirhodium Catalysts That Bear Redox Noninnocent Chelating Dicarboxylate Ligands and Their Performance in Intra- and Intermolecular C–H Amination (pages 562–568)

      Katherine P. Kornecki and John F. Berry

      Article first published online: 17 NOV 2011 | DOI: 10.1002/ejic.201100814

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      Two new analogues of the well-knownC–H amination catalyst [Rh2(esp)2] (esp =α,α,α′,α′-tetramethyl-1,3-benzenedipropanoate) are reported that bear redox-active supporting ligands that are structurally similar to esp. The dissimilar electrochemistry of the three catalysts and their different performance in intra-/intermolecular reactions support two mechanisms for the C–H amination reaction.

    12. C–H Bond Amination

      Insights into the Mechanism of the Ruthenium–Porphyrin-Catalysed Allylic Amination of Olefins by Aryl Azides (pages 569–580)

      Daniela Intrieri, Alessandro Caselli, Fabio Ragaini, Piero Macchi, Nicola Casati and Emma Gallo

      Article first published online: 15 NOV 2011 | DOI: 10.1002/ejic.201100763

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      The [Ru(TPP)CO]-catalysed synthesis of allylic amines was performed by employing aryl azides (ArN3) as nitrogen sources. A mechanistic hypothesis for the nitrene transfer reaction to cyclohexene was proposed on the basis of synthetic, spectroscopic and kinetic studies.

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