European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 29

October 2014

Volume 2014, Issue 29

Pages 4908–5083

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. You have free access to this content
      Unprecedented Borylene Insertion into a C–N Bond (Eur. J. Inorg. Chem. 29/2014)

      Rajendra S. Ghadwal, Christian J. Schürmann, Felix Engelhardt and Christian Steinmetzger

      Article first published online: 10 OCT 2014 | DOI: 10.1002/ejic.201490144

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      The cover picture shows insertion of a borylene into a C–N bond with an N-heterocyclic olefin (NHO) ligand. Selective borylene insertion into a C–N bond to yield boryl-functionalized NHOs [{N(Dipp)N(DippBH)CHCH}CCH2]2 and [{N(Dipp)N(DippBPh)CHCH}CCH2][{N(Dipp)N(2-iPr-6-CHMeCH2BC6H3)CHCH}CCH2] (Dipp = 2,6-iPr2C6H3) is reported for the first time. (IPrCH2)BHCl2 affords completely unexpected diborane compound (IPr)BH2BH2(IPr). Lewis acid induced ring opening of THF to form the borenium ion [(IPrCH2)B{O(CH2)4I}2]I is demonstrated. Details are discussed in the Short Communication by R. S. Ghadwal et al. on p. 4921 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. You have free access to this content
      Unprecedented Borylene Insertion into a C–N Bond (page 4908)

      Rajendra S. Ghadwal, Christian J. Schürmann, Felix Engelhardt and Christian Steinmetzger

      Article first published online: 10 OCT 2014 | DOI: 10.1002/ejic.201402872

      Thumbnail image of graphical abstract

      Insertion of a borylene into a C?N bond is reported for the first time...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 4921 ff.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. Graphical Abstract: Eur. J. Inorg. Chem. 29/2014 (pages 4909–4914)

      Article first published online: 10 OCT 2014 | DOI: 10.1002/ejic.201490145

  4. News

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
  5. Masthead

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. Masthead: Eur. J. Inorg. Chem. 29/2014 (pages 4919–4920)

      Article first published online: 10 OCT 2014 | DOI: 10.1002/ejic.201490147

  6. Short Communication

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. Borylene Insertion

      Unprecedented Borylene Insertion into a C–N Bond (pages 4921–4926)

      Rajendra S. Ghadwal, Christian J. Schürmann, Felix Engelhardt and Christian Steinmetzger

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402750

      Thumbnail image of graphical abstract

      Formation of a boryl-functionalized NHO 6 as a dimer suggests the involvement of a borylene insertion into a C–N bond. The parent borylene (R = H) follows a completely different route in which hydrogen abstraction and intermolecular B–B coupling events seem operative to afford a diborane (7) stabilized by an NHC.

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. Spin-Crossover Complexes

      Unusual Solvent Dependence of a Molecule-Based FeII Macrocyclic Spin-Crossover Complex (pages 4927–4933)

      Hongfeng Wang, Chiara Sinito, Abdellah Kaiba, José Sanchez Costa, Cédric Desplanches, Philippe Dagault, Philippe Guionneau, Jean-François Létard, Philippe Negrier and Denise Mondieig

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402666

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      The solvent dependence of spin-crossover behavior and metastability of the FeII complex [FeL222N3O2(CN)2]·H2O were investigated. Compared with the pristine and the dehydrated complex, the rehydrated complex shows enhanced metastability and an increased spin-transition temperature. This solvent dependence indicates new possibilities to improve metastability toward further applications.

    2. Coordination Chemistry

      Evolution of the Coordination-Sphere Symmetry in Copper(II), Nickel(II), and Zinc(II) Complexes with N,N′-Double-Armed Diaza-Crown Ethers: Experimental and Theoretical Approaches (pages 4934–4945)

      Katalin Selmeczi, Jean-Pierre Joly, Mustapha Allali, Violeta Yeguas, Bernard Henry and Manuel Ruiz-Lopez

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402432

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      Symmetric versus asymmetric octahedral coordination geometry changes were observed for Cu2+, Ni2+, and Zn2+ complexes of a N,N′-triazolyl-biarmed diaza[18]crown-6 macrocycle. Quantum chemical calculations at the DFT level confirmed these observations and allowed us to interpret them in terms of covalent or noncovalent metal–ligand interactions.

    3. Copper Catalysis

      Tetranuclear Copper(II) Complexes with Macrocyclic and Open-Chain Disiloxane Ligands as Catalyst Precursors for Hydrocarboxylation and Oxidation of Alkanes and 1-Phenylethanol (pages 4946–4956)

      Mirela-Fernanda Zaltariov, Mihaela Alexandru, Maria Cazacu, Sergiu Shova, Ghenadie Novitchi, Cyrille Train, Anatolie Dobrov, Marina V. Kirillova, Elisabete C. B. A. Alegria, Armando J. L. Pombeiro and Vladimir B. Arion

      Article first published online: 18 AUG 2014 | DOI: 10.1002/ejic.201402578

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      Two new tetranuclear copper(II) complexes act as homogeneous catalyst precursors for the single-pot hydrocarboxylation of a variety of linear and cyclic Cn (n = 5–8) alkanes into the corresponding Cn+1 carboxylic acids, peroxidative oxidation of cyclohexane, and solvent-free microwave-assisted oxidation of 1-phenylethanol.

    4. Anionic Ligands

      Nickel and Copper Complexes of Pyrrolecarboxamide Ligands – Stabilization of M3+ Species and Isolation of Ni3+ Complexes (pages 4957–4965)

      Sushil Kumar, Megha Munjal, Jyoti Singh and Rajeev Gupta

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402361

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      NiII and CuII complexes of pyrrolecarboxamide ligands containing –H, –CH3, and –Cl substituents are presented. Chemical and electrochemical oxidation results in the isolation of Ni3+ complexes and the generation of Cu3+ species. Spectroscopic studies reveal square-planar geometries around the Ni3+ and Cu3+ ions.

    5. Catalytic Networks

      Two-Dimensional {Co3+–Co2+} and {Fe3+–Co2+} Networks and Their Heterogeneous Catalytic Activities (pages 4966–4974)

      Sumit Srivastava, Manvender Singh Dagur and Rajeev Gupta

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402375

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      Reusable two-dimensional {Co3+–Co2+} and {Fe3+–Co2+} networks heterogeneously catalyze Knoevenagel condensation and cyanation reactions of assorted aldehydes owing to the kinetic lability and Lewis acidity of the secondary Co2+ ions.

    6. Janus-Head NHC Ligands

      Mono- and Hetero-Dinuclear Complexes of Janus-Head NHC Ligands Possessing Backbone Phosphinoyl Groups: the Case of Soft and Hard Metal Centers (pages 4975–4983)

      Paresh Kumar Majhi, Spencer C. Serin, Gregor Schnakenburg, Derek P. Gates and Rainer Streubel

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402440

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      A family of hybrid ligands composed of hard phosphine oxides and soft N-heterocyclic carbene donor sites have been employed to synthesize [M(cod)Cl(NHCP)] complexes I, which were further converted into the corresponding dicarbonyl complexes in order to study their donor properties. The advantage of backbone phosphinoyl groups was exploited to generate hetero-dinuclear TiIV, RhI complexes 10a,a′.

    7. Schiff-Base Complexes

      Main-Chain Oligomers from NiII- and CuII-Centered Unsymmetrical N2O2 Schiff-Base Complexes: Synthesis and Spectral, Structural, and Second-Order Nonlinear Optical Properties (pages 4984–4993)

      Salvador Celedón, Vincent Dorcet, Thierry Roisnel, Anu Singh, Isabelle Ledoux-Rak, Jean-René Hamon, David Carrillo and Carolina Manzur

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402469

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      The esterification of binuclear phenol and carboxylic acid functionalized ferrocenyl-containing metal-centered Schiff-base complexes (M = Ni, Cu) in the presence of N,N′-dicyclohexylcarbodiimide and dmap afforded their corresponding main-chain oligomers. They are formed of approximately six monomeric units, are redox active, and exhibit good thermal stability and high second-order NLO responses.

    8. Trimetallic Ag Complexes

      Triangular [Ag3]3+ Complexes Supported by Picolyl-Substituted N-Heterocyclic Carbene Ligands (pages 4994–5007)

      Lyndsay B. Munro and Vincent J. Catalano

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402483

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      A series of 12 picolyl-substituted benzimidazolylidene- and imidazolinylidene-based N-heterocyclic carbene ligands have been prepared. Eleven underwent complexation with AgI to form trimetallic complexes with short AgI–AgI metal–metal separations. In solution, all but one of these complexes are dynamic and dissociate and exchange ligands.

    9. Cluster Compounds

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      Mixed-Metal Oxo Clusters Structurally Derived from Ti6O4(OR)8(OOCR′)8 (pages 5008–5014)

      Christine Artner, Ayse Koyun, Matthias Czakler and Ulrich Schubert

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402499

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      Fe/Ti, Zn/Ti, Cd/Ti, Ca/Ti, and Sr/Ti mixed-metal oxo clusters were obtained from the reaction of titanium alkoxides with the corresponding metal acetates and methacrylic acid. Their structures can be traced back to that of Ti6O4(OR)8(OOCR′)8 clusters and the structural variations to the different ionic radii and coordination numbers.

    10. Cation Structures

      Protonated Digermane, Distannane, and Diplumbane: Can They Be Made in the Laboratory? (pages 5015–5020)

      Yundong Guo, Yanjun Hao, Hui Wang, Yaoming Xie and Henry F. Schaefer III

      Article first published online: 20 AUG 2014 | DOI: 10.1002/ejic.201402510

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      Similarly to C2H7+ and Si2H7+, the Ge2H7+, Sn2H7+, and Pb2H7+ cations are predicted to be energetically favorable to varying degrees, and they appear to have different low-lying structures.

    11. Multinuclear Complexes

      Tetranuclear Nickel and Cobalt Complexes with an Incomplete Double-Cubane Structure – Homo- and Heterometallic Complexes and Their 1D Coordination Polymers (pages 5021–5033)

      Takayuki Nakajima, Keiko Seto, Andreas Scheurer, Bunsho Kure, Takashi Kajiwara, Tomoaki Tanase, Masahiro Mikuriya and Hiroshi Sakiyama

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402536

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      Unsymmetrical amine-diol ligands are suitable for the assembly of homo- and heterometallic tetranuclear {M4O6} complexes. 1D coordination polymers are formed by linking the tetranuclear nickel and cobalt complexes with a diol linker ▪▪((<=Author: the size of the graphic for the table of contents had to be reduced for technical reasons))▪▪.

    12. Inclusion Compounds

      Synthesis, Characterisation and Antiproliferative Studies of Allyl(dicarbonyl)(cyclopentadienyl)molybdenum Complexes and Cyclodextrin Inclusion Compounds (pages 5034–5045)

      Susana S. Braga, Vijaya Mokal, Filipe A. Almeida Paz, Martyn Pillinger, Ana F. Branco, Vilma A. Sardão, Cátia V. Diogo, Paulo J. Oliveira, Maria P. M. Marques, Carlos C. Romão and Isabel S. Gonçalves

      Article first published online: 19 AUG 2014 | DOI: 10.1002/ejic.201402540

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      The crystal structure of [(η5-C5H4–COOH)Mo(CO)23-C3H5)] (1) is presented. Both 1 and its phenylalanine derivative were included into β-cyclodextrin (CD) and per-O-methylated β-CD (TRIMEB). Overall, the inclusion contributed to a higher and more specific action on tumour cells, thereby lowering deleterious effects on a healthy myoblast line.

    13. Mechanism of Palladium Catalysis

      Mechanistic Insights into the PdII-Catalyzed Chemoselective N-Demethylation vs. Cyclometalation Reactivity Pathways in 1-Aryl-N,N-dimethylethanamines (pages 5046–5052)

      Jeanette See Leng Yap, Yi Ding, Xiang-Yuan Yang, Jonathan Wong, Yongxin Li, Sumod A. Pullarkat and Pak-Hing Leung

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402547

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      Two structurally isomeric substituted N,N-dimethylethanamines have been prepared. Treatment of one isomer with PdII ions generated the ortho-metalated complex, whilst the other isomer resulted in the unexpected chemoselective C–N bond cleavage to afford the corresponding secondary amine.

    14. Ambiphilic Ligands

      Synthesis, Structures and Coordination Chemistry of Singly Bridged Phosphane-Boranes with Coordinately Unsaturated Platinum Group Metals (pages 5053–5062)

      Victoria K. Greenacre, Melvyn B. Ansell, S. Mark Roe and Ian R. Crossley

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402649

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      The synthesis and characterisation of a range of singly bridged phosphane-boranes is described. Their coordination complexes with co-ordinately unsaturated platinum group metals demonstrate a propensity for adopting structures with pendant borane moieties occupying distal positions.

    15. Heterogeneous Catalysis

      The Nature of the Active Site in Ziegler–Natta Olefin Polymerization Catalysis Systems – A Computational Investigation (pages 5063–5076)

      Jugal Kumawat, Virendra Kumar Gupta and Kumar Vanka

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402180

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      The nature of the active site in Ziegler–Natta heterogeneous catalysis systems has been explored with density functional theory (DFT). New insights include the understanding that donor coordination to the metal center can lead to an increase in the molecular weight of the polymer. The role of AlEt3 as a possible donor has also been investigated.

    16. Asymmetric Strecker Reaction

      Chiral MnIII–salalen and –salan Complexes Derived from (S)-Pyrrolidin-2-ylmethanamine and Their Catalytic Activity in the Asymmetric Strecker Reaction (pages 5077–5083)

      Pramod Kumar, S. Saravanan, Noor-ul Hasan Khan, Firasat Hussain and Surendra Singh

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402548

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      Chiral MnIII–salalen and –salan complexes have been synthesized and used as a catalyst for the asymmetric Strecker reaction. These complexes were characterized by elemental analysis, FTIR and UV/Vis spectroscopy, exact mass determination and single-crystal XRD. The catalyst 9a catalysed the Strecker reactions of a range of substrates with moderate enantioselectivity of the corresponding products.

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