DOCSLIB.ORG

Reduction Chemistry of Neptunium Cyclopentadienide Complexes: from Structure to Cite This: Chem

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Reduction Chemistry of Neptunium Cyclopentadienide Complexes: from Structure to Cite This: Chem Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Reduction chemistry of neptunium cyclopentadienide complexes: from structure to Cite this: Chem. Sci.,2017,8,2553 understanding† Michał S. Dutkiewicz,ab Christos Apostolidis,a Olaf Walter*a and Polly L. Arnold*b Neptunium complexes in the formal oxidation states II, III, and IV supported by cyclopentadienyl ligands are explored, and significant differences between Np and U highlighted as a result. A series of neptunium(III) cyclopentadienyl (Cp) complexes [Np(Cp)3], its bis-acetonitrile adduct [Np(Cp)3(NCMe)2], 0 0 anditsKCpadductK[Np(Cp)4]and[Np(Cp)3](Cp ¼ C5H4SiMe3) have been made and characterised III providing the first single crystal X-ray analyses of Np Cp complexes. In all NpCp3 derivatives there are 5 III three Cp rings in h -coordination around the Np centre; additionally in [Np(Cp)3] and K[Np(Cp)4]one 1 Cp ring establishes a m-h -interaction to one C atom of a neighbouring Np(Cp)3 unit. The solid state structure of K[Np(Cp)4] is unique in containing two different types of metal–Cp coordination III 5 Creative Commons Attribution 3.0 Unported Licence. geometries in the same crystal. Np (Cp)4 units are found exhibiting four units of h -coordinated Cp IV rings like in the known complex [Np (Cp)4], the structure of which is now reported. A detailed comparison of the structures gives evidence for the change of ionic radii of ca. À8pmassociatedwith change in oxidation state between NpIII and NpIV. The rich redox chemistry associated with the 0 syntheses is augmented by the reduction of [Np(Cp )3]byKC8 in the presence of 2.2.2-cryptand to II II afford a neptunium(II) complex that is thermally unstable above À10 C like the U and Th complexes Received 4th January 2017 K(2.2.2-cryptand)[Th/U(Cp0) ]. Together, these spontaneous and controlled redox reactions of organo- Accepted 27th January 2017 3 neptunium complexes, along with information from structural characterisation, show the relevance of DOI: 10.1039/c7sc00034k organometallic Np chemistry to understanding fundamental structure and bonding in the minor This article is licensed under a rsc.li/chemical-science actinides. nuclei.6–8 For example, recent quantitative carbon K-edge X-ray Open Access Article. Published on 30 January 2017. Downloaded 15/05/2017 13:43:43. Introduction absorption spectroscopy (XAS) analyses on the organometallic ¼ “ ” Fiy years have passed since the foundation of organometallic [An(COT)2] (An Th, U), actinocenes provided the rst neptunium chemistry in the form of cyclopentadienyl chem- experimental evidence for extensive 4-orbital interactions in istry,1 and yet only a handful of complexes have been reported, thorocene, and remarkably little in the U analogue, with con- 9 and even fewer fully characterised.2–4 Yet increasingly, trasting trends in orbital mixing. Furthermore, a combination combined synthetic/spectroscopic/computational studies are of experimental and QTAIM computational comparisons of demonstrating how covalently binding, so, carbocyclic [M(LAr)X] (M ¼ Sm, U, Np; X ¼ Cl, I; LAr ¼ dianionic arene- 10 organometallic ligands that form actinide-ligand s-, p-, d- and bridged trans-calix[2]benzene[2]pyrrole ) showed signicant even 4-(back)bonding interactions provide an excellent plat- differences (up to 17%) in orbital contributions to M–L bonds form for advancing the fundamental understanding of the between the Ln and An analogues, and that the covalency in the differences in orbital contributions and covalency in f-block Np–ligand bonding arises from spatial orbital overlap rather 4 metal–ligand bonding.5 Understanding the subtleties are key to than a coincidental energy degeneracy. The work also demon- the safe handling and separations of the highly radioactive strated differences between U and Np in their reaction chem- istry, such as the stability of the NpII formal oxidation state or IV III aEuropean Commission, Directorate for Nuclear Safety and Security, Joint Research the reduction of Np to Np upon complexation. Centre, Postfach 2340, D-76125, Karlsruhe, Germany. E-mail: Olaf.Walter@ec. Organoneptunium chemistry has relied heavily on the À europa.eu ubiquitous cyclopentadienyl ligand, Cp ¼ (C5H5) , as a strongly bEaStCHEM School of Chemistry, The University of Edinburgh, Joseph Black Building, binding, sterically demanding yet exible, monoanion, and David Brewster Road, Edinburgh, EH9 3FJ, UK. E-mail: [email protected] focused almost exclusively on NpIV complexes. The rst † Electronic supplementary information (ESI) available: General procedures, ¼ evidence for the formation of [Np(Cp)3X] (X Cl, F) came from synthetic details, spectroscopic data, X-ray crystallographic data. CCDC 238 1524162–1524166. For ESI and crystallographic data in CIF or other electronic a radiochemical synthesis, i.e. the irradiation of a U complex 1 ¼ format see DOI: 10.1039/c7sc00034k with thermal neutrons, and [Np(Cp)3X] (X Cl, F) were This journal is © The Royal Society of Chemistry 2017 Chem. Sci.,2017,8, 2553–2561 | 2553 View Article Online Chemical Science Edge Article subsequently reported from standard chemical routes as Results thermally robust, volatile complexes.11,12 Baumg¨artner et al. re- Syntheses ported the rst homoleptic organoneptunium complex, tetrak- h5 is( -cyclopentadienyl)neptunium(IV), [Np(Cp)4], from All the syntheses start from NpCl4. This can be directly trans- 13 treatment of NpCl4 with excess KCp in benzene. Many of the formed into [Np(Cp)4], NpCp4 by the reaction of NpCl4 with an 13 earliest studies on neptunium cyclopentadienyl complexes also excess of KCp in toluene. Single crystals of NpCp4 grow in the had the aim of exploring covalency in the bonding, using the supernatant during a prolonged extraction of the crude product fact that Np is a Mossbauer¨ active nucleus. However, not all the with pentane. The spectroscopic data agree with the literature 12,23 NpCp – 11,12 studies agreed. The rst Mossbauer¨ studies on [Np(Cp)4] and reports. 4 itself can be from a reaction with NH4Cl – NpCp Cl [Np(COT)2] suggested less interaction between the central ion converted to [Np(Cp)3Cl], 3 which is an ideal starting – and the Cp ligands but appreciable covalency in the Np COT material for the synthesis of [Np(Cp)3], NpCp3. The reduction of 14 12 bonding. On the other hand, Bohlander reported the isomer NpCp3Cl by Na/Hg in Et2Oaffords NpCp3 as its diethyl ether shi of the Np nucleus in [Np(Cp)4] closely approaches that of solvate [Np(Cp)3(Et2O)], Scheme 1. This solvent molecule is the record-breaking, covalent [Np(COT)2], thus being the most labile and can be easily removed in vacuum to afford the solvent covalent Np–Cp derivative. Finally, from analysis of the isomer free NpCp3 which is only sparingly soluble in non-coordinating shis Karraker14,15 stated that there were smaller covalent solvents due to the polymeric nature of the molecular structure bonding contributions in [Np(Cp)4] than [Np(Cp)3Cl], whereas (see below) but dissolves slowly in Et2O, THF, or MeCN, 16,17 Adrian concluded the opposite. again forming solvates [Np(Cp)3(Et2O)], [Np(Cp)3(THF)], or The redox properties of the element play a pivotal role in [Np(Cp)3(NCMe)2], NpCp3(NCMe)2, respectively. neptunium chemistry as it conventionally exhibits ve oxida- Crystals of [Np(Cp)3(Et2O)] could not be analysed via X-ray tion states in compounds, from +3 to +7.18 Recently, we reported diffraction as during the crystal mounting procedure they lose II Ar Ar that a formally Np complex Np(L )(dme) supported by L , the coordinated Et2O solvent molecule readily. Similarly, no stable Creative Commons Attribution 3.0 Unported Licence. trans-calix[2]benzene[2]pyrrole is accessible; black solutions adducts of a lanthanide analogue [Ln(Cp)3(OEt2)] have yet been were sufficiently stable (up to 90 minutes) for spectroscopic reported. However, single crystals of the bis-acetonitrile adduct analyses but crystals were too small for single crystal diffraction NpCp3(NCMe)2 have been grown from acetonitrile solution at analyses.4 Somewhat surprisingly, given the increased stability RT and studied by X-ray diffraction. III III of the Np oxidation state compared to U , this work was also The reaction of NpCp3Cl with 1.1 equiv. of KCp in THF does the rst to report single crystal structural studies on organo- not lead to the simple Cl substitution product NpCp4.Aer 4 metallic NpIII complexes. To date, the only organometallic NpIV dreux and evaporation of the solvent, n-pentane extraction complexes characterised by single crystal X-ray diffraction recovered half of the starting material NpCp3Cl (49%), and 2,19 20 are neptunocene [Np(C8H8)2], [Np(Cp)Cl3(OPPh2Me)2], a subsequent extraction with Et2Oafforded maroon single crys- This article is licensed under a 21 III K[NpCp ] [Np(Cp)3(OPh)], and two examples of the Cp3Np-functional- tals of the new, reduced, Np complex K[Np(Cp)4], 4 in ised adduct [(UO2)(THF)(H2L)] (L ¼ ‘Pacman’ Schiff-base 37% yield. When the reaction is repeated without heating the 3 polypyrrolic macrocycle), in which we studied the Cp3Np mixture, no soluble, molecular product can be isolated. NpCp0 Open Access Article. Published on 30 January 2017. Downloaded 15/05/2017 13:43:43. coordination to one oxo group of the uranyl dication to compare For the synthesis of [Np(C5H4SiMe3)3], 3 another the degree of electron transfer via the oxo-bridge between U, Np, reaction pathway was followed as no starting material [Np(C5- III and Pu cations. Structurally characterised Np organometallics H4SiMe3)3Cl] was available: NpCl3 is generated in situ from the Ar 4 are still limited to the [M(L )X] complexes we reported.
Load more

Recommended publications
  • Controlling Ligand Substitution Reactions of Organometallic Complexes: Tuning Cancer Cell Cytotoxicity
    Controlling ligand substitution reactions of organometallic complexes: Tuning cancer cell cytotoxicity Fuyi Wang*, Abraha Habtemariam*, Erwin P. L. van der Geer*, Rafael Ferna´ ndez*, Michael Melchart*, Robert J. Deeth†, Rhona Aird‡, Sylvie Guichard‡, Francesca P. A. Fabbiani*, Patricia Lozano-Casal*, Iain D. H. Oswald*, Duncan I. Jodrell‡, Simon Parsons*, and Peter J. Sadler*§ *School of Chemistry, University of Edinburgh, West Mains Road, EH9 3JJ Edinburgh, United Kingdom; †Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom; and ‡CRUK Pharmacology and Drug Development Team, University of Edinburgh Cancer Research Centre, Cancer Research UK Oncology Unit, Crewe Road South, EH4 2XR Edinburgh, United Kingdom Edited by Jack Halpern, University of Chicago, Chicago, IL, and approved October 27, 2005 (received for review July 11, 2005) Organometallic compounds offer broad scope for the design of the factors that control the aqueous chemistry of organometallic therapeutic agents, but this avenue has yet to be widely explored. complexes may therefore also allow the design of effective A key concept in the design of anticancer complexes is optimization anticancer agents. of chemical reactivity to allow facile attack on the target site (e.g., Our studies are focused on monofunctional ruthenium(II) arene DNA) yet avoid attack on other sites associated with unwanted anticancer complexes of the type [(␩6-arene)Ru(ethylenediamin- side effects. Here, we consider how this result can be achieved for e)(X)]nϩ, where X is a leaving group (e.g., Cl). In these pseudooc- monofunctional ‘‘piano-stool’’ ruthenium(II) arene complexes of tahedral ‘‘piano-stool’’ RuII complexes, a ␲-bonded arene (the the type [(␩6-arene)Ru(ethylenediamine)(X)]n؉.
    [Show full text]
  • Cyclic Voltammetry of Mono- and Diiron(II)Cyclopentadienyl Complexes of Thianthrene and Related Heterocycles R
    Subscriber access provided by University of Texas Libraries Cyclic voltammetry of mono- and diiron(II)Cyclopentadienyl complexes of thianthrene and related heterocycles R. Quin Bligh, Roger Moulton, Allen J. Bard, Adam Piorko, and Ronald G. Sutherland Inorg. Chem., 1989, 28 (13), 2652-2659 • DOI: 10.1021/ic00312a030 Downloaded from http://pubs.acs.org on January 30, 2009 More About This Article The permalink http://dx.doi.org/10.1021/ic00312a030 provides access to: • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Inorganic Chemistry is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 2652 Inorg. Chem. 1989, 28, 2652-2659 nate-bond formation, not only for the metal-dioxygen bond but constant reported by Baker et al." For CoSALTMEN, the ox- also for the coordinate bonds between the metal ion and the ligand ygenation constant found here for diglyme solution at 0.5 "C is donor atoms. The increase in the electropositive nature of the very small, ca. -3.5, while the value reportedI2 for DMAC solution metal ion on oxygenation results in strengthening of its coordinate at 5 OC is similar, ca. -3.4. These low values, which seem to be bonds, thus contributing considerably to the exothermicity of the lower than those of any other cobalt Schiff base complexes re- reaction. All entropies of oxygenation are seen to be negative, ported, may indicate steric effects resulting from the distortion a general characteristic for all oxygenation processes. The observed from planarity of the ligand by the four methyl substituents on decrease of entropy is considered derived from two sources: (1) the ethylene bridge.
    [Show full text]
  • Organometallics Study Meeting H.Mitsunuma 1
    04/21/2011 Organometallics Study Meeting H.Mitsunuma 1. Crystal field theory (CFT) and ligand field theory (LFT) CFT: interaction between positively charged metal cation and negative charge on the non-bonding electrons of the ligand LFT: molecular orbital theory (back donation...etc) Octahedral (figure 9-1a) d-electrons closer to the ligands will have a higher energy than those further away which results in the d-orbitals splitting in energy. ligand field splitting parameter ( 0): energy between eg orbital and t2g orbital 1) high oxidation state 2) 3d<4d<5d 3) spectrochemical series I-< Br-< S2-< SCN-< Cl-< N -,F-< (H N) CO, OH-< ox, O2-< H O< NCS- <C H N, NH < H NCH CH NH < bpy, phen< NO - - - - 3 2 2 2 5 5 3 2 2 2 2 2 < CH3 ,C6H5 < CN <CO cf) pairing energy: energy cost of placing an electron into an already singly occupied orbital Low spin: If 0 is large, then the lower energy orbitals(t2g) are completely filled before population of the higher orbitals(eg) High spin: If 0 is small enough then it is easier to put electrons into the higher energy orbitals than it is to put two into the same low-energy orbital, because of the repulsion resulting from matching two electrons in the same orbital 3 n ex) (t2g) (eg) (n= 1,2) Tetrahedral (figure 9-1b), Square planar (figure 9-1c) LFT (figure 9-3, 9-4) - - Cl , Br : lower 0 (figure 9-4 a) CO: higher 0 (figure 9-4 b) 2. Ligand metal complex hapticity formal chargeelectron donation metal complex hapticity formal chargeelectron donation MR alkyl 1 -1 2 6-arene 6 0 6 MH hydride 1 -1 2 M MX H 1 -1 2 halogen 1 -1 2 M M -hydride M OR alkoxide 1 -1 2 X 1 -1 4 M M -halogen O R acyl 1 -1 2 O 1 -1 4 M R M M -alkoxide O 1-alkenyl 1 -1 2 C -carbonyl 1 0 2 M M M R2 C -alkylidene 1 -2 4 1-allyl 1 -1 2 M M M O C 3-carbonyl 1 0 2 M R acetylide 1 -1 2 MMM R R C 3-alkylidine 1 -3 6 M carbene 1 0 2 MMM R R M carbene 1 -2 4 R M carbyne 1 -3 6 M CO carbonyl 1 0 2 M 2-alkene 2 0 2 M 2-alkyne 2 0 2 M 3-allyl 3 -1 4 M 4-diene 4 0 4 5 -cyclo 5 -1 6 M pentadienyl 1 3.
    [Show full text]
  • Structural Analysis of Zincocenes with Substituted Cyclopentadienyl Rings
    DOI: 10.1002/chem.200801917 Structural Analysis of Zincocenes with Substituted Cyclopentadienyl Rings Rafael Fernndez,[a] Abdessamad Grirrane,[a] Irene Resa,[a] Amor Rodrguez,[a] Ernesto Carmona,*[a] Eleuterio lvarez,[a] Enrique Gutirrez-Puebla,[b] ngeles Monge,[b] Juan Miguel Lpez del Amo,[c] Hans-Heinrich Limbach,[c] Agustí Lleds,[d] Feliu Maseras,[d, e] and Diego del Ro[a, f] Abstract: New zincocenes [ZnCp’2](2– tion of 7, which yields a side-product ZnÀC bond of comparable strength to 5) with substituted cyclopentadienyl li- (C) upon attempted crystallisation. the ZnÀMe bond in ZnMe2. Zincocene gands C5Me4H, C5Me4tBu, Compounds 5 and 6 were also investi- 5 has dynamic behaviour in solution, 13 5 1 C5Me4SiMe2tBu and C5Me4SiMe3, re- gated by C CPMAS NMR spectrosco- but a rigid h /h (s) structure in the spectively, have been prepared by the py. Zincocenes 1 and 2 have infinite solid state, as revealed by 13C CPMAS reaction of ZnCl2 with the appropriate chain structures with bridging Cp’ li- NMR studies, whereas for 6 the differ- Cp’-transfer reagent. For a comparative gands, while 3 and 4 exhibit slipped- ent nature of the Cp’ ligands and of the structural study, the known sandwich geometries. Compounds 5 ring substituents of the h1-Cp’ group 5 1 [Zn(C5H4SiMe3)2](1), has also been in- and 6 have rigid, h /h (s) structures, in (Me and SiMe3) have permitted obser- 5 vestigated, along with the mixed-ring which the monohapto C5Me4SiMe3 vation for the first time of the rigid h / ACHTUNGRE 1 zincocenes [Zn(C5Me5)(C5Me4SiMe3)] ligand is bound to zinc through the h solution structure.
    [Show full text]
  • Synthesis and Reactivity of Cyclopentadienyl Based Organometallic Compounds and Their Electrochemical and Biological Properties
    Synthesis and reactivity of cyclopentadienyl based organometallic compounds and their electrochemical and biological properties Sasmita Mishra Department of Chemistry National Institute of Technology Rourkela Synthesis and reactivity of cyclopentadienyl based organometallic compounds and their electrochemical and biological properties Dissertation submitted to the National Institute of Technology Rourkela In partial fulfillment of the requirements of the degree of Doctor of Philosophy in Chemistry by Sasmita Mishra (Roll Number: 511CY604) Under the supervision of Prof. Saurav Chatterjee February, 2017 Department of Chemistry National Institute of Technology Rourkela Department of Chemistry National Institute of Technology Rourkela Certificate of Examination Roll Number: 511CY604 Name: Sasmita Mishra Title of Dissertation: ''Synthesis and reactivity of cyclopentadienyl based organometallic compounds and their electrochemical and biological properties We the below signed, after checking the dissertation mentioned above and the official record book(s) of the student, hereby state our approval of the dissertation submitted in partial fulfillment of the requirements of the degree of Doctor of Philosophy in Chemistry at National Institute of Technology Rourkela. We are satisfied with the volume, quality, correctness, and originality of the work. --------------------------- Prof. Saurav Chatterjee Principal Supervisor --------------------------- --------------------------- Prof. A. Sahoo. Prof. G. Hota Member (DSC) Member (DSC) ---------------------------
    [Show full text]
  • Book of Abstracts-1
    Volume: 3 ISMEC GROUP SERIES Year: 201 3 http:// mat520.unime.it/ismecacta/ Symposium Edition: XXI V ISSN : 2239 -2459 *Acta of the International Simposia on Metal Complex *Acta of the International Simposia on Metal Complex Begoña García , Editor Facultad de Ciencias, Universidad de Burgos, Spain President of the Scientific Committee of ISMEC201 3 Guido Crisponi, Editor University of Cagliari, Italy President of the ISMEC group ISMEC GROUP SERIES Volume: 3 Year: 201 3 ISSN: 2239-2459 Symposium Edition: XXI V Sponsors /Collaborators The following institutions and companies have supported ISMEC201 3, which we acknowledge: Sponsors : Collaborators : The Acta of the International Symposia on Metal Complexes (ISSN: 2239-2459) are published annually online by the ISMEC Group. Editors : Begoña García (President of the Scientific Committee of ISMEC 2013) Departamento de Química Facultad de Ciencias Universidad de Burgos Plaza de Missael Bañuelos s/n 09001 Burgos (Spain) [email protected] Guido Crisponi (President of the ISMEC Group) Dipartimento di Scienze Chimiche Università degli Studi di Cagliari Cittadella Universitaria 09042 Monserrato – Cagliari, ITALY [email protected] Scientific Committee of ISMEC 2013: Begoña García (University of Burgos, Spain) Guido Crisponi (University of Cagliari, Italy) Antonio Bianchi (University of Florence, Italy) Etelka Farkas (University of Debrecen, Hungary) Enrique García-España (University of Valencia, Spain) Carlos C.F. Geraldes (University of Coimbra, Portugal) Juan Niclós (University of Granada, Spain) Henryk
    [Show full text]
  • 1 Signature Page Biphenyl Substituted Cyclopentadienyl Ligand
    Signature page Biphenyl substituted Cyclopentadienyl Ligand Complexes By Ketnavi Ramgoolam A Thesis Submitted to Saint Mary’s University, Halifax, Nova Scotia in Partial Fulfillment of the Requirements for the Degree of Bachelor of Science Degree with Honours in Chemistry April 2019, Halifax, Nova Scotia Copyright Ketnavi Ramgoolam, 2019. Approved: Dr. Jason Masuda Supervisor Department of Chemistry Date: April 24, 2019 1 Biphenyl substituted Cyclopentadienyl Ligand Complexes By Ketnavi Ramgoolam A Thesis Submitted to Saint Mary’s University, Halifax, Nova Scotia in Partial Fulfillment of the Requirements for the Degree of Bachelor of Science Degree with Honours in Chemistry April 2019, Halifax, Nova Scotia Copyright Ketnavi Ramgoolam, 2019. Approved: Dr. Jason Masuda Supervisor Department of Chemistry Date: April 24, 2019 2 Biphenyl substituted Cyclopentadienyl Ligand Complexes by Ketnavi Ramgoolam Abstract The synthesis of biphenyl substituted cyclopentadienyl ligands are described. The synthetic route is accomplished through the reaction of aryl lithium reagents with cobaltocenium salts, followed by oxidation of the intermediate cobalt(I) species to give the corresponding cyclopentadiene. Detailed information on their preparation, structural, and spectroscopic properties are described. A preliminary reaction towards the biphenyl substituted cyclopentadienyl ligand complexes yielding the corresponding alkali metal salt (K) is also described. Its structural and spectroscopic properties are described briefly. March 20, 2019 3 Acknowledgements First of all, I would like to express my most sincere gratitude to my supervisor, Dr. Jason Masuda, for all of his time, efforts, teachings and guidance. Thank you for being a most wonderful and understanding human being. This project helped me in discovering my potential as a chemist and I had plenty of wonderful experiences and opportunities that I personally believe will forever shape and influence my professional life as well as my personal growth.
    [Show full text]
  • Progress in Inorganic Chemistry Volume 59 Advisory Board
    Progress in Inorganic Chemistry Volume 59 Advisory Board JACQUELINE K. BARTON CALIFORNIA INSTITUTE OF TECHNOLOGY, PASADENA, CALIFORNIA SHUNICHI FUKUZUMI OSAKA UNIVERSITY, OSAKA, JAPAN CLARK R. LANDIS UNIVERSITY OF WISCONSIN, MADISON, WISCONSIN NATHAN S. LEWIS CALIFORNIA INSTITUTE OF TECHNOLOGY, PASADENA, CALIFORNIA STEPHEN J. LIPPARD MASSACHUSETTS INSTITUTE OF TECHNOLOGY, CAMBRIDGE, MASSACHUSETTS JEFFREY R. LONG UNIVERSITY OF CALIFORNIA, BERKELEY, CALIFORNIA THOMAS E. MALLOUK PENNSYLVANIA STATE UNIVERSITY, UNIVERSITY PARK, PENNSYLVANIA TOBIN J. MARKS NORTHWESTERN UNIVERSITY, EVANSTON, ILLINOIS JAMES M. MAYER YALE UNIVERSITY, NEW HAVEN, CONNECTICUT DAVID MILSTEIN WEIZMANN INSTITUTE OF SCIENCE, REHOVOT, ISRAEL WONWOO NAM EWHA WOMANS UNIVERSITY, SEOUL, KOREA VIVIAN W. W. YAM UNIVERSITY OF HONG KONG, HONG KONG PROGRESS IN INORGANIC CHEMISTRY Edited by Kenneth D. Karlin DEPARTMENT OF CHEMISTRY JOHNS HOPKINS UNIVERSITY BALTIMORE,MARYLAND VOLUME 59 Cover Design: Wiley Copyright 2014 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jersey. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750–8400, fax (978) 750–4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748–6011, fax (201) 748–6008, or online at http://www.wiley.com/go/ permission.
    [Show full text]
  • Ligand David Peter Klein Iowa State University
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 2004 Chemistry of ruthenium complexes incorporating the doubly-linked bis(dimethylsilylcyclopentadienyl) ligand David Peter Klein Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Klein, David Peter, "Chemistry of ruthenium complexes incorporating the doubly-linked bis(dimethylsilylcyclopentadienyl) ligand " (2004). Retrospective Theses and Dissertations. 1138. https://lib.dr.iastate.edu/rtd/1138 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Chemistry of ruthenium complexes incorporating the doubly-linked bis(dimethylsilylcyclopentadienyl) llgand by David Peter Klein A thesis submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Inorganic Chemistry Program of Study Committee: Robert J. Angel ici, Major Professor Victor Lin Gordon J. Miller Marc Porter Mark S. Gordon Iowa State University Ames, Iowa 2004 UMI Number: 3145699 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted.
    [Show full text]
  • Cyclopentadienyl Ruthenium Chemistry
    ln+õe CV C LOPENT AOTENV L RUÍHEÑTUM CHEMTSÍRY *** bq Robu,t Cha¡Le's wa,U'U 8.Sc. lHows.) r** A The'si's pneterttød {on thø løgnøe od OocÅon o( Plvílc:.sop|tq Thø Oeytantnønf o( PLtqaLcal and InongawLe Cheni'sfnq The. UwLvetui-tq o6 Ade-La,Ldø Junø I98l I ,\ - I f l, . 1, ,-ei Jì ;.-', ,ìi I ì v'ri.t, -, i{ .f f¡. I 'i i, Ì i,.ov'ao,i.l. ¡t r i,', , j.l , il I ì:1r,'ì ' ,,1,{ ., TAßLE OF CONÍENTS SECTÍON A. CHAPTER 1. A SUMMARY OF THE CHEMISTRV OF CARB(0NYL.FREE COMPLEXES OT THE TYPE RuX(PRs) z(n-CsHs ). Røa"e-LLowt o d tltø l'le,tß..L- tla'Logøn Bond 5 Líga.nd Exelnng ø Røacfio nt 6 Ca.tionie CompX.exe's I Røaetíoyu o[ RuR(PPhs)z (n-Csfls ) t0 (A) Cqc,[.omefa'L[-a-.tion R¿ac.tiorø 10 (B) Rza.cfion¿ w,í,th EX-øcfnctn-dø(¡icLenf. )Lødiru t4 and A,Llzqne.r Aeutq[idø CompLexe's 29 CHAPTER 2, CV C L??ENT AO T ENV L-RUT HENI UMt AN, - 0SMI UI,l CHEtr {I STRV, 3)îÁPLEXES C0NTA/^JING NITRILES, IS0NITRILES, TERTIARy PÍI0SPINES ANO PHOSPHTTES F,RMEO ßY AYOTTTON ()R DTSPLACE¡,,IENT REACT/ONS. lntnoducbLon 3l ReacÍ.cowt wí.th N'í.tní,Le's 32 RearLLon wífh TnLdluonoa"ce,tovt/if)ú't-e- 38 R¿ae,LLont a$(ond"Lng l¿oru.Í¡i.(-e Comp,Lexe's 43 Røq.oLLon's wi-th Te,nLLanq Pho,sphine's a"nd Phodptuíføt 45 Oi'scu.¿¿ion 49 Expwínønta.L 53 0HATrER 3, CV C L?PENT AOI ENV L-RUT HENI Ul,tl AN, - OSM I ul'l CHEMI STRV .
    [Show full text]
  • Answers to Exercises References Abbreviations
    ANSWERS TO EXERCISES REFERENCES ABBREVIATIONS INDEX ATOMIC WEIGHTS OF THE ELEMENTS PERIODIC TABLE OF THE ELEMENTS ANSWERS TO EXERCISES CHAPTER 1 + + 1.1. [FeCp2] , sandwich structure with parallel rings, [FeL4X2] , 17, 5, 3, 6; [RhCl(PPh3)3], square planar, [RhL3X], 16, 8, 1, 4; [Ta(CH2CMe3)3(CHCMe3)], tetrahedral, [TaX5], 10, 0, 5, 4; [ScCp*2(CH3)], bent sandwich with CH3 in the equatorial plane, [ScL4X3], 14, 0, 3, 7; [HfCp2Cl2], bent sandwich with both Cl ligands in the equatorial plane, [HfL4X4], 16, 0, 4, 8; – – [W(H)(CO)5] , octahedral, [WL5X] , 18, 6, 0, 6; 2 2+ 2+ [Os(NH3)5( -C6H6)] , octahedral, [OsL6] , 18, 6, 2, 6; [Ir(CO)(PPh3)2(Cl)], square planar, [IrL3X], 16, 8, 1, 4; [ReCp(O)3], pseudo-octahedral, [ReL2X7], 18, 0, 7, 6; 2– 2– [PtCl4] , square planar, [PtX4] , 16, 8, 2, 4; – – [PtCl3(C2H4)] , square planar, [PtLX3] , 16, 8, 2, 4; [CoCp2], sandwich structure with parallel rings, [CoL4X2], 19, 7, 2, 6; 6 [Fe( -C6Me6)2], sandwich structure with parallel rings, [FeL6], 20, 8, 0, 6; [AuCl(PPh3)], linear, [AuLX], 14, 10, 1, 2; 4 [Fe( -C8H8)(CO)3], trigonal bipyramid (piano stool), [FeL5], 18, 8, 0, 5; 1 2+ 2+ [Ru(NH3)5( -C5H5N)] , octahedral, [RuL6] , 18, 6, 2, 6; 2 + + [Re(CO)4( -phen)] , octahedral, [(ReL6] , 18, 6, 1, 6; + + [FeCp*(CO)(PPh3)(CH2)] , pseudo-octahedral (piano stool), [(FeL4X3] , 18, 6, 4, 6; 2+ 2+ [Ru(bpy)3] , pseudo-octahedral, [RuL6] , 18, 6, 2, 6. 2 1.2. In the form [FeCp*( -dtc)2], both dithiocarbamate ligands are chelated to iron, 2 1 [FeL4X3], 19, 5, 3, 7.
    [Show full text]
  • Piano-Stool N-Heterocyclic Carbene Iron Complexes: 2 Synthesis, Reactivity and Catalytic Applications 3
    1 Piano-Stool N-Heterocyclic Carbene Iron Complexes: 2 Synthesis, Reactivity and Catalytic Applications 3 4 Chloe Johnson, Martin Albrecht* 5 6 Department of Chemistry & Biochemistry University of Bern Freiestrasse 3, 3012 Bern 7 (Switzerland) 8 Fax: (+41) 31-6314644; E-mail: [email protected] 9 10 Abstract. This review summarises the advances of N-heterocyclic carbenes (NHCs) as ligands 11 to iron half-sandwich complexes, often referred to as piano-stool complexes because of their 12 structural motif. The review introduces various synthetic routes towards this sub-class of NHC 13 iron-complexes including in particular direct and transmetallation strategies as well as the 14 synthesis of the carbene directly within the iron coordination sphere. Many of these complexes 15 have demonstrated promising reactivity that is relevant to the arenas of catalysis and materials 16 chemistry. In particular, bond activation (e.g. C–H, Si–H, H–H) processes provide exciting 17 new opportunities to exploit these systems for stoichiometric and catalytic transformations. 18 Substantial advances have been achieved specifically in the catalytic reduction of unsaturated 19 substrates, and this topic is emphasised in particular. | downloaded: 27.12.2020 20 https://doi.org/10.7892/boris.105921 21 source: 1 Content 2 1. Introduction 3 2. Synthetic Routes towards Piano-Stool NHC Iron Complexes 4 2.1. Thermal activation of enetetramines 5 2.2. Transmetallation 6 2.3. Arene bonding to Fe(NHC) synthon 7 2.4. Free carbene route 8 2.5. Internal base (aminolysis) route 9 2.6. Formation of NHC within the iron coordination sphere 10 2.7.
    [Show full text]