DOCSLIB.ORG

ANNEX IV. WG's Annual Summary

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
ANNEX IV. WG's Annual Summary ANNEX IV. WG’s annual summary (6) WG D36/001/06 Annual report Project title: Redox activity of host-guest, organometallic and molecular structures at electrode interfaces. II. Scientific report The joint research of host-guest complexes included the synthesis of several derivatives, in which the permethylated cyclodextrins were attached covalently to fullerene. The fullerene moiety was attached to the primary and also to the secondary cyclodextrin rings. Solubility of these compounds in water enabled us investigation of redox reactions of C60 in protic medium. The objective was the distinction of an intramolecular complexation from interactions C60-cyclodextrin between two molecules by electrochemical methods. Results were jointly published in Carbon. The redox activity of pesticides containing the nitroaromatic group is significantly increased by cationic catalysis. The joint research included very low frequency electrochemical impedance measurements combined with the modeling. We proved that under certain conditions the catalyzed electron transfer gives rise to the negative differential resistance. Such heterogeneous redox system yields spontaneous electric oscillations. Hence it is a suitable model system for natural periodic reactions. Results were jointly published in Electrochemica Acta. A series of new spiral-shaped organic dications was synthesized. The structure– properties relationships were sought in a series of [5]helquats having different number of methyl substitutents in several positons of aromatic rings. This study proved possible tuning of redox properties for applications of helquats as redox transfer mediators. Furthermore, these compounds were thoroughly investigated by EPR and electrochemical techniques seeking distinction between the formation of a charge transfer complexe and a complete electron transfer. The publication was accepted to Phys. Chem. Chem. Phys. journal The application of in-situ spectroelectrochemical methods involves a close cooperation with D35 action. Both partner laboratories achieved numerous results in the field 1 of interfacial organometallic redox chemistry. This yielded a review article in a high-impact journal. The combination of the reaction-oriented electrochemistry with the species-focussed spectroscopy in spectroelectrochemistry (SEC) allows a more complete analysis of electron transfer processes and redox reactions in general. Selected examples involving UV-VIS-NIR and IR absorption spectroscopy as well as electron paramagnetic resonance (EPR) illustrate the potential and the applicability of this technique. Original results obtained this year are described below. Research of the electron transfer in new organometallic compounds included phosphorescent cyclometalated heteroleptic iridium(III) phenylpyridinato (ppy) complexes containing luminescent 1-pyridylimidazo [1,5-α]pyridine (pip) ligands. Excitation of + [[Ir(ppy)2 (pip)] in acetonitrile solutions at room temperature results in a dual luminescence, strongly quenched by O2. Four complexes show, in absence of O2, a high-energy emission (assigned to a 3MLLCT transition) with two maxima in the blue region of the visible spectra, and a second structured emission (assigned largely to a 3LC π–π* transition. New tris(ferrocenylcopper) compounds {(µ3-dqp)[Cu(dppf)]3}(BF4)3, dppf = 1,1’- bis(diphenylphosphinoferrocene), dqp = hexamethyl-, hexachloro- and un-substituted diquinoxalino[2,3-a:2’,3’-c]phenazine = hexaazatrinaphthylene (HATN), undergo at least two differently separated reversible one-electron reductions and three very closely spaced one- electron oxidations. While the latter are attributed to the stepwise ferrocene→ferrocenium conversions, the first electron addition occurs in the ligand bridge to yield EPR detectable radical complexes. Reversible steps reveal very low energy transitions for the reduced forms in agreement with the frontier MO arrangement. Our WG published 7 papers and 9 congress presentations with abstracts. Two STSM were granted. Seven other exchange visits were financed from other local sources. Publications: 1. L. Pospíšil, M. Hromadová, M. Gál, J. Bulíčková, R. Sokolová, S. Filippone, J. Yang, Z. Guan, A. Rassat, Y. Zhang Redox Potentials and Binding Enhancement of Fullerene and Fullerene-Cyclodextrin Systems in Water and Dimethylsulfoxide. Carbon, 48 (2010) 153. 2. M. Hromadová, L. Pospíšil, R. Sokolová, N. Fanelli New electrochemical oscillator based on the cation-catalyzed reduction of nitroaromatic radical anions. Electrochim. Acta, 54 (2009), 4991 2 3. L. Adriaenssens, L. Severa, T. Šálová, I. Císařová, R. Pohl, D. Šaman, S. V. Rocha, N. S. Finney, L. Pospíšil, P. Slavíček, F. Teplý Helquats: A Facile, Modular, Scalable Route to Novel Helical Dications Chemistry Eur. J., 15 (2009) 1072. 4. L. Pospíšil, M. Hromadová, M. Gál, M. Valášek, N. Fanelli, V. Kolivoška Irregular Polarographic Currents Obey Feigenbaum Universality Route from Order to Chaos Coll. Czechoslovak Chem. Commun, DOI: 10.1135/cccc2009120 5. G. Volpi, C. Garino, L. Salassa, J. Fiedler, K. I. Hardcastle, R. Gobetto, C. Nervi Cationic Heteroleptic Cyclometalated Iridium Complexes with 1-Pyridylimidazo [1,5- α]Pyridine Ligands: Exploitation of an Efficient Intersystem Crossing Chem. Eur. J, 15 (2009), 6415. 6. S. Roy, B. Sarkar, C. Duboc, J. Fiedler, O. Sarper, F. Lissner, S. M. Mobin, G. K. Lahiri, W. Kaim Heterohexanuclear (Cu3Fe3) Complexes of Substituted Hexaazatrinaphthylene - (HATN) Ligands: Twofold BF4 Association in the Solid and Stepwise Oxidation (3 e) or Reduction (2 e) to Spectroelectrochemically Characterized Species Chem. Eur. J. 15 (2009), 6932 7. W. Kaim, J. Fiedler Spectroelectrochemistry: the best of two worlds Chem. Soc. Rev. 38 (2009), 3373 Congress presentations and abstracts: 1. R. Sokolová, M. Hromadová, J. Ludvík, L. Pospíšil, S. Giannarelli: “ The Autoprotolysis in Reduction Mechanism of Substituted Benzonitriles“ in The 60th Annual Meeting of the International Society of Electrochemistry, Symposium S10 – Molecular Electrochemistry: In its own right and in service to related research areas, Cd of Abstracts, Beijing, China, August 16 – 21, 2009, p 8. 2. L. Pospíšil, M. Gál, , M. Hromadová, R. Sokolová, J. Bulíčková, Y. Zhang , A. Rassat, S. Filippone, J. Yang, Z. Guan: ”Water-Soluble Fullerene Compounds Facilitate Nitrogen Fixation“ in The 60th Annual Meeting of the International Society of Electrochemistry, Symposium S10 – Molecular Electrochemistry: In its own right and in service to related research areas, Cd of Abstracts, Beijing, China, August 16 – 21, 2009, p 29. 3. M. Hromadová, L. Pospíšil, R. Sokolová, S. Giannarelli, M. Gál: “ Focus on the Fate of Bifenox Anion Radical in the Presence of Cyclodextrin Cavities“ in The 60th Annual Meeting of the International Society of Electrochemistry, Symposium S10 – Molecular Electrochemistry: In its own right and in service to related research areas, Cd of Abstracts, Beijing, China, August 16 – 21, 2009, p 42. 4. R. Sokolová, I. Degano, M. Valášek, J. Fiedler, M. Hromadová, L. Pospíšil, J. Bulíčková, M. Gál, M. P. Colombini: „The Oxidation of Natural Dye Quercetin“ in International Symposium on Frontiers of Electrochemical Science and Technology, Book of Abstracts, Xi’an, August 12 – 15, 2009, O08. 5. V. Kolivoška, M. Valášek, L. Pospíšil, R. Sokolová, M. Hromadová: „On the Adsorption of Extended Viologens at the Mercury-Solution Interface.“ in International Symposium on Frontiers of Electrochemical Science and Technology, Book of Abstracts, Xi’an, China, August 12 – 15, 2009, O14. 6. L. Pospíšil, F. Teplý, M. Gál, L. Adriaenssens, M. Horáček, L. Severa, ElectronTransfer in Helical Polyaromatics in International Symposium on Frontiers of Electrochemical 3 Science and Technology, Book of Abstracts, Xi’an, China, August 12 – 15, 2009, O06. 7. L. Pospíšil, M. Gál, M. Horáček, F. Teplý, L. Adriaenssens, L. Severa, Structure- Reactivity Relationships in Electron Transfers of Helical Polyaromatic Dications, COST Chemistry D36 Workshop, Structural-performance relationships at the surface of functional materials, Book of Abstracts, Benahavis, Malaga, Spain, 21.-23.10.2009, p.123. 8 Z. Guan, J. Yang, Y. Wang, F. Moussa, L. Pospíšil, Y. Zhang, Synthesis of novel 2:1 permethyulated-cyclodextrin-fullerene conjugates, COST Chemistry D36 Workshop, Structural-performance relationships at the surface of functional materials, Book of Abstracts, Benahavis, Malaga, Spain, 21.-23.10.2009, p.141. 9. G. Volpi, J. Fiedler, L. Pospíšil, M. Sandroni, C. Garino, R. Gobetto, G. Viscardi, C. Nervi, Electrochemical functionalization of glassy carbon electrode surfaces by organometallic moieties. COST Chemistry D36 Workshop, Structural-performance relationships at the surface of functional materials, Book of Abstracts, Benahavis, Malaga, Spain, 21.-23.10.2009, p.143 II A Innovative networking Participating laboratories gained a certaindegree of an innovative knowledge from sharing expertize in different fields. One example is the publication [1]. Previous research by a laboratory specialized in synthesis could not resolve a problem of supramolecular protection of reactive forms of fullerene. A joint experiments brought results by performing high sensitivity low-frequency impedance measurements, which could discriminate subtle effects of intramolecular interactions. It is expected that those derivatives may find application on pharmacology and other fields. The COST action promoted launching national and bilateral projects involving several institutes participating in this D36 project.
Load more

Recommended publications
  • UNIVERSITY of CALIFORNIA, SAN DIEGO Photoinduced Mixed
    UNIVERSITY OF CALIFORNIA, SAN DIEGO Photoinduced mixed-valency and delocalization dynamics in strongly coupled multinuclear ruthenium complexes A dissertation submitted in partial satisfaction of the requirements for the degree Doctor of Philosophy in Chemistry by Jane Susan Henderson Committee in charge: Professor Clifford Kubiak, Chair Professor Andrew Kummel Professor Melvin Okamura Professor Stanley Opella Professor Michael Tauber 2015 Copyright © Jane Henderson, 2015 All rights reserved. The Dissertation of Jane Susan Henderson is approved, and it is acceptable in quality and form for publication on microfilm and electronically: –––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– –––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– –––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– –––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– –––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– Chair University of California, San Diego 2015 iii Dedication For my parents. iv Epigraph Go to bed smarter than when you woke up. –Charlie Munger v TABLE OF CONTENTS Signature Page ....................................................................................................................... iii Dedication .............................................................................................................................. iv Epigraph ................................................................................................................................
    [Show full text]
  • Oxidation of Ferrocene Derivatives with Dibenzoyl Peroxide and Meta-Chloroperoxybenzoic Acid
    Cleveland State University EngagedScholarship@CSU ETD Archive 2018 Oxidation of Ferrocene Derivatives with Dibenzoyl Peroxide and Meta-Chloroperoxybenzoic Acid Jos M. Halstead Cleveland State University Follow this and additional works at: https://engagedscholarship.csuohio.edu/etdarchive Part of the Chemistry Commons, and the Medicine and Health Sciences Commons How does access to this work benefit ou?y Let us know! Recommended Citation Halstead, Jos M., "Oxidation of Ferrocene Derivatives with Dibenzoyl Peroxide and Meta- Chloroperoxybenzoic Acid" (2018). ETD Archive. 1108. https://engagedscholarship.csuohio.edu/etdarchive/1108 This Dissertation is brought to you for free and open access by EngagedScholarship@CSU. It has been accepted for inclusion in ETD Archive by an authorized administrator of EngagedScholarship@CSU. For more information, please contact [email protected]. OXIDATION OF FERROCENE DERIVATIVES WITH DIBENZOYL PEROXIDE AND META-CHLOROPEROXYBENZOIC ACID JOSHUA M. HALSTEAD Bachelor of Science in Chemistry Cleveland State University May 2011 Master of Science in Chemistry Cleveland State University May 2013 submitted in partial fulfillment of requirements for the degree DOCTOR OF PHILOSOPHY IN CLINICAL AND BIOANALYTICAL CHEMISTRY at the CLEVELAND STATE UNIVERSITY DECEMBER 2018 DEDICATION This work is dedicated to Dr. John Masnovi, who sadly passed away shortly before its completion. I will remember him for his insightful instruction, kind demeanor, and willingness to help anyone learn. He will be missed. We hereby approve this dissertation for Joshua M. Halstead Candidate for the Doctor of Philosophy in Clinical-Bioanalytical Chemistry degree for The Department of Chemistry and the CLEVELAND STATE UNIVERSITY’S College of Graduate Studies by _________________________________________________________________ Dissertation Chairperson, Dr.
    [Show full text]
  • Supplementary Information
    Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013 Supplementary Information Mechanochemical and silica gel-mediated formation of highly electron-poor 1-cyanocarbonylferrocene Daniel Nieto,a Sonia Bruña,a M. Merced Montero-Campillo,b Josefina Perles, c Ana Mª González-Vadillo,*a Julia Méndez,a Otilia Mo,*b and Isabel Cuadrado*a a Departamento de Química Inorgánica, bDepartamento de Química, c Servicio Interdepartamental de Investigación, c Universidad Autónoma de Madrid, Facultad de Ciencias, Cantoblanco, 28049, Madrid, Spain. E-mail: [email protected] 1. General Experimental Details 2 2. Synthetic Procedures 3 2.1. Synthesis of 1-cyanomethylferrocene FcCH2CN (1) 3 2.2. Mechanochemical synthesis of 1-cyanocarbonylferrocene FcC(O)CN (2) 3 3. Structural Characterization of Compounds 1 and 2 4 Figures S1 and S2: 1H NMR and 13C NMR spectra of 1 4 Figures S3 and S4: IR spectrum of 1 and IR spectra (in KBr) of a powered mixture of 1 and SiO2, measured at different times of grinding 5 1 Figures S5 and S6: Comparison of H NMR of 1, 1 + SiO2 (after 1h) and 2 and 1H NMR spectrum of 2 6 Figures S7 and S8: 13C NMR spectrum and IR spectrum of 2 7 Figures S9 and S10: Mass spectrum (EI) of 2 8 4. UV-Visible Studies 9 Figure S11: Comparison of the UV-Visible spectra of FcCH2CN (1), FcC(O)CN (2), FcCN and Ferrocene 9 5. Crystallographic Data for Compounds 1 and 2 10 Table S1: Sample and crystal data for FcCH2CN (1) 10 Figures S12 and S13: Molecular structure and crystal-packing diagram of 1 10 Table S2: Sample and crystal data for FcC(O)CN (2) 12 Figure S14 and S15: Molecular Structure and Crystal-packing diagram of 2 12 6.
    [Show full text]
  • Surface Passivation and Positive Band-Edge Shift of P-Si(111)
    Subscriber access provided by Caltech Library C: Surfaces, Interfaces, Porous Materials, and Catalysis Surface Passivation and Positive Band-Edge Shift of p-Si(111) Surfaces Functionalized with Mixed Methyl/Trifluoromethylphenylacetylene Overlayers Miguel Cabán-Acevedo, Kimberly M. Papadantonakis, Bruce S. Brunschwig, and Nathan S. Lewis J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.0c02017 • Publication Date (Web): 30 Jun 2020 Downloaded from pubs.acs.org on June 30, 2020 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
    [Show full text]
  • Oxidation Kinetics of Ferrocene Derivatives with Dibenzoyl Peroxide
    Journal of Organometallic Chemistry 880 (2019) 39e46 Contents lists available at ScienceDirect Journal of Organometallic Chemistry journal homepage: www.elsevier.com/locate/jorganchem Oxidation kinetics of ferrocene derivatives with dibenzoyl peroxide * Joshua M. Halstead a, Refaat Abu-Saleh a, Steven M. Schildcrout b, , John Masnovi a, 1 a Department of Chemistry, Cleveland State University, Cleveland, OH, 44115, USA b Department of Chemistry, Youngstown State University, Youngstown, OH, 44555, USA article info abstract Article history: Chemical oxidation of ferrocene and related derivatives by dibenzoyl peroxide in acetonitrile solution Received 27 September 2018 produces ferrocenium and benzoic acid after acidification. The rate law is first order in oxidant and in Received in revised form reductant. Steric effects and activation parameters are consistent with a rate-controlling outer-sphere 18 October 2018 single-electron transfer (ET) step, and reorganization energies are obtained using Marcus theory with Accepted 25 October 2018 B3LYP calculations. Energetics, optimized structures, and solvent effects indicate that rate is affected Available online 27 October 2018 more by anion than cation solvation and that oxidation of decamethylferrocene by 3- chloroperoxybenzoic acid does not occur by ET. Keywords: © Ferrocene 2018 Elsevier B.V. All rights reserved. Peroxide Kinetics Single-electron transfer Marcus theory B3LYP calculation 1. Introduction application [7]. Additional work is needed to understand the mechanisms regarding the activity and peroxide-driven inactiva- Peroxide oxidations of iron compounds are important and tion of such enzymes to improve their properties, such as by pro- ubiquitous processes. One example is Fenton's reagent. This system, tein engineering. which combines catalytic ferrous iron with hydroperoxides, has Ferrocenes provide simpler models to investigate oxidations of attracted considerable attention for its capability to destroy envi- Fe(II).
    [Show full text]
  • Download File
    Design of functional materials from molecular building blocks Anastasia Voevodin Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences Columbia University 2019 © 2019 Anastasia Voevodin All rights reserved ABSTRACT Design of functional materials from molecular building blocks Anastasia Voevodin This dissertation is a summary of my research developing the synthesis and assembly of functional materials from nanoscale building blocks and studying their emergent properties. Chapter 1 introduces superatoms as exciting atomically precise supramolecular building blocks for materials design. Bottom-up assembly of these superatoms into materials with increased dimensionality (0D, 1D, 2D, and 3D) offers exciting opportunities to create novel solid-state compounds with tailored functions for widespread technological applications. I review recent advances to assemble superatomic materials and focus on assemblies from metal chalcogenide clusters and fullerenes. In subsequent chapters, I employ several of these nanoscale superatoms as the precursors to functional materials. Chapter 2 describes the synthesis and structural characterization of a hybrid solid-state compound assembled from two building blocks: a nickel telluride superatom and an endohedral fullerene. Although a varied library of binary superatomic solids has been assembled from fullerenes, this is the first demonstration of a superatomic assembly using an endohedral fullerene as a building block. Lu3N@C80 fullerenes are dimerized in this new solid-state compound with an unpreceded orientation of the encapsulated metal nitride cluster. I explore the structural characterization of this material supported with computational evidence to explain the dimerization and orientation of the endohedral fullerenes. In Chapter 3 I begin to detail my exploration into assembling superatoms at micro and meso-scales –which will be the focus of Chapters 3-5.
    [Show full text]
  • Oxygen and Hydrogen Peroxide Reduction by 1,2-Diferrocenylethane
    Journal of Electroanalytical Chemistry 681 (2012) 16-23. © 2012 by authors and © 2012 Elsevier. Preprinted by permission of Elsevier. Oxygenandhydrogenperoxidereductionby1,2-diferrocenylethane atliquid/liquidinterface Haiqiang Dengaǡ Pekka Peljobǡ Fernando Cortés-Salazaraǡ Peiyu Geaǡ Kyösti KontturibǡHubertH.Giraulta,* aLaboratoire d’Electrochimie Physique et Analytique, Ecole Polytechnique FédéraledeLausanne(EPFL),Station6,CH-1015Lausanne,Switzerland bDepartmentofChemistry,AaltoUniversity,P.O.Box16100,00076,Finland * CORRESPONDING AUTHOR FOOTNOTE E-mail: [email protected] Telephone number: +41-21-693 3145 Fax number: +41-21-693 3667 Acceptedmanuscript Journal of Electroanaytical Chemistry, 681 (2012) 16-23. http://www.sciencedirect.com/science/article/pii/S1572665712001907 1 Abstract: Molecular oxygen and hydrogen peroxide reduction by 1,2-diferrocenylethane (DFcE) was investigated at polarized water/1,2-dichloroethane (W/DCE) interface. The overall reaction points to proton-coupled electron transfer (PCET)mechanism,wherethefirststepconsistsoftheprotonationofDFcEto formtheDFcE-H+inDCEphase,eitherbyDFcEfacilitatedprotontransferacross the liquid-liquid interface or by the homogeneous protonation of DFcE in the presence of protons extracted in the oil phase by tetrakis(pentafluorophenyl)borate.TheformationofDFcE-H+isfollowedupby theO2reductiontohydrogenperoxideandfurtherreductiontowater.Thefinal productsofDFcEoxidation,namelyDFcE+or DFcE2+ǡwereinvestigatedbyion transfer voltammetry, ultramicroelectrode voltammetry and UV/visible
    [Show full text]
  • On Choosing Ferrocene As an Internal Reference Redox Scale for Voltammetric Measurements: a Cautionary Tale
    Medicinal & Analytical Chemistry International Journal ISSN: 2639-2534 On Choosing Ferrocene as an Internal Reference Redox Scale for Voltammetric Measurements: A Cautionary Tale Angel AJ Torriero* Mini Review School of Life and Environmental Sciences, Deakin University, Australia Volume 3 Issue 4 Received Date: November 25, 2019 *Corresponding author: Angel A J Torriero, School of Life and Environmental Published Date: December 18, 2019 Sciences, Deakin University, Burwood, Victoria 3125, Australia, Tel: +61392446897; DOI: 10.23880/macij-16000151 Email: [email protected] Abbreviations: CV: Cyclic Voltammetry. transfer to be a simple one-electron outer-sphere electron transfer. Introduction It is very important that the IRRS redox moieties do not specifically interact with the working electrode (e.g., Internal reference redox scales or internal reference they do not adsorb on the working electrode). redox systems, IRRS, are reversible or nearly reversible The mid-point potential for the IRRS should not overlap redox systems used to provide a known and stable the active potential zone of the analyte (ANS) under reference point in non-aqueous solvents in conditions study. where reliable reference electrodes are difficult to be The initially present IRRS redox component, OXIRRS or established and/or stabilized [1,2]. In general, the IRRS is REDIRRS, must be stable over the time period of used in conjunction with quasi-reference electrodes [3-8]. experimentation; it should not react (or interact) with They have a long story, which began with the concept of the solvent, supporting electrolyte or ANS. Rb|Rb+ or Rb(Hg)|Rb+, followed by the use of The IRRS redox moiety, OXIRRS or REDIRRS, which is not organometallic redox couples [9].
    [Show full text]
  • Binuclear Metal Complexes of a Doubly Bridged Cyclopentadienyl Ligand'
    1328 Organometallics 1992, 11, 1328-1333 Binuclear Metal Complexes of a Doubly Bridged Cyclopentadienyl Ligand' Ulrich Siemeling, Peter Jutzi, Beate Neumann,t and Hans-Georg Stammlert FakuWt fur Chemle der Universitlit, Universitlitsstrasse, W4800 Bielefehl 1, Federal Republic of Germany Michael B. Hursthouset Chemistry Department, Queen Mary and WestfieM College, London E 1 4NS, Unlted Kingdom Received July 19, 199 1 Binuclear metal complexes derived from the doubly bridged cyclopentadiene system 2,2,8,8-tetra- methyl-2,8-di~ilatricyclo[7.3.O.O3~7]dodeca-3,5,9,ll-tetraene(LH,) are examined. This compound is de- protonated with 2 equiv of l-butyllithiumto form the dilithio salt LLi2 (2). Reaction of 2 with trimethyltin chloride yields (Me&&L (3). The analogous reaction with Cp*RuCl (Cp* = C5Me5)gives the binuclear ruthenocene (Cp*Ru)& (4). By cocomplexation of 2 and Cp*Li with iron(I1) chloride, the binuclear ferrocene (Cp*Fe)& (5) is obtained. Reaction of LH2with odawbonyldicobalt leads to the formation of [(CO)2Co]2L (6). The analogous reaction with pentacarbonyliron yields a mixture of products, from which [(C0)2Fe]2L (FeFe) (7) is isolated. The stereochemistry of complexes 3-7 is investigated by IR and NMR spectroscopy. Single-crystal X-ray structure determinations are performed for 5 and 6. The structure investigations on 5 show a trans arrangement of the two Cp*Fe units. The ligand L is not planar. The unit cell contains two independtnt molecules, whose bonding parameters are essentially identical (crystal system triclinic; space group P1; a = 8.7443 (13),A, b = 18.561 (3) A, c = 20.576 (4) A; CY = 89.340 (13)O, B = 89.160 (13)O, y = 78.300 (12)O; 2 = 4).
    [Show full text]
  • Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior Towards Cobalt and Iron Carbonyl Compounds
    Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior towards Cobalt and Iron Carbonyl Compounds von der Fakultät für Naturwissenschaften der Technischen Universität Chemnitz genehmigte Dissertation zur Erlangung des akademischen Grades doctor rerum naturalium (Dr. rer. nat.) Vorgelegt von M.Sc. Grzegorz Paweł Filipczyk Geboren am. 07.01.1966 in Chorzów (Polen) eingereicht am: 31.05.2017 Erstgutachter: Prof. Dr. Heinrich Lang Zweitgutachter: Prof. Dr. Klaus Stöwe Tag der Verteidigung: 04.12.2017 ii Bibliografische Beschreibung und Referat Filipczyk, Grzegorz Paweł Ferrocenyl-Alkine und Butadiine: Reaktionsverhalten gegenüber Cobalt- und Eisencarbonyl-verbindungen Technische Universität Chemnitz, Fakultät für Naturwissenschaften Dissertation, 2017, 155 Seiten. Die vorliegende Dissertation beschreibt die Synthese und Charakterisierung von neuartigen perferrocenylierten, cyclischen Komplexen unter Anwendung der Cobalt- vermittelten Cyclomerisierung in Kombination mit einer C-H-Bindungsaktivierung als auch die Bildung von ferrocenylierten Phosphinoalkinid-Komplexen mit Eisen- und Cobaltcarbonylen. Die elektrochemischen Eigenschaften und die Elektronentransfer- prozesse zwischen den terminalen Ferrocenyleinheiten in den unterschiedlichen cyclischen Verbindungen wurden unter Einbeziehung der Struktur/chemischen Zusammensetzung der Brückenbausteine ermittelt. Elf perferrocenylierte, cyclische Komplexe wurden mittels [2+2] bzw. [2+2+2] 5 5 Cyclomerisierung von 1,4-Diferrocenylbutadiin FcC≡C–C≡CFc (Fc = Fe(η -C5H4)(η - 5 C5H5)) unter Verwendung
    [Show full text]
  • The First Isolable Low-Valent Ferrocene Enabling the Application
    The First Isolable Low-valent Ferrocene Enabling the Application of Unprecedented Ferrocene Anolyte Authors: Hayoung Song1*, Giyun Kwon2, Cooper Citek3, Seungwon Jeon1, Kisuk Kang,2,4,5‡ and Eunsung Lee1,6‡ Affiliations: 1 Department of Chemistry, Pohang University of Science and Technology. Pohang, 37673, Republic of Korea. 2 Department of Materials Science and Engineering, Research Institute of Advanced Materials (RIAM), Seoul National University, 1 Gwanak Road, Seoul 151-742, Republic of Korea. 3 Division of Chemistry and Chemical Engineering, California Institute of Technology (Caltech), Pasadena, California 91125, United States. 4 Institute of Engineering Research, College of Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea. 5 Center for Nanoparticle Research, Institute of Basic Science, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea. 6 Division of Advanced Materials Science, Pohang University of Science and Technology. Pohang, 37673, Republic of Korea. ‡Correspondence to: [email protected] (E.L.) and [email protected] (K.K). *Current Address: Center for Self-Assembly and Complexity (CSC), Institute for Basic Science (IBS), Pohang, 37673, Republic of Korea. Abstract: Here, we report the first isolable low-valent biscyclopentadienyl iron complexes stabilized by NHC-functionalized ligands (NHC-Cps), which were characterized by electron paramagnetic resonance (EPR) and 57Fe Mössbauer spectroscopy. Additional theoretical studies on these formally low-valent ferrocene complexes clearly explain the origin of their thermodynamic stability and the orbital interactions between iron and NHC-Cp. Exploiting the facile Fe(II/I) redox chemistry, we successfully demonstrated that the NHC-Fc compounds can be applied as the first example of ferrocene anolyte for redox-flow batteries.
    [Show full text]
  • Pyrrolinium-Substituted Persistent Zwitterionic Ferrocenate De
    Pyrrolinium-substituted Persistent Zwitterionic Ferrocenate De- rivative Enabling the Application of Ferrocene Anolyte Authors: Hayoung Song1, Giyun Kwon2, Cooper Citek3, Seungwon Jeon1, Kisuk Kang,2,4,5‡ and Eunsung Lee1,6‡ Affiliations: 1 Department of Chemistry, Pohang University of Science and Technology. Pohang, 37673, Republic of Korea. 2 Department of Materials Science and Engineering, Research Institute of Advanced Materials (RIAM), Seoul National University, 1 Gwanak Road, Seoul 151-742, Republic of Korea. 3 Division of Chemistry and Chemical Engineering, California Institute of Technology (Caltech), Pasadena, California 91125, United States. 4 Institute of Engineering Research, College of Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea. 5 Center for Nanoparticle Research, Institute of Basic Science, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea. 6 Division of Advanced Materials Science, Pohang University of Science and Technology. Pohang, 37673, Republic of Korea. ‡ Correspondence to: [email protected] (E.L.) and [email protected] (K.K). ABSTRACT: Here, we report the imidazolium-/pyrrolinium-substituted persistent zwitterionic ferrocenate derivatives, which were characterized by electron paramagnetic resonance (EPR) and 57Fe Mössbauer spectroscopy. Additional theoretical studies on these zwitterionic ferrocenate derivatives clearly explain the origin of their thermal stability and the orbital interactions between iron and imidazolium-/pyrrolinium-substituted zwitterionic cyclopentadienyl ligand. Exploiting the facile Fe(II/I) redox chemistry, we successfully demonstrated that the ferrocene derivative can be ap- plied as an example of derivatized ferrocene anolyte for redox-flow batteries. These zwitterionic ferrocenate deriva- tives will not only deepen our understanding of the intrinsic chemistry of ferrocenate but have the potential to open the way for the rational design of metallocenate derivatives for various applications.
    [Show full text]