Electronic Structure and Bonding in Pyrrolic Macrocycle-Supported Complexes of Actinides
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Application with the Even-Odd Rule and a Specific Periodic Table for Organic and Inorganic Atoms
Open Journal of Physical Chemistry, 2021, 11, 54-63 https://www.scirp.org/journal/ojpc ISSN Online: 2162-1977 ISSN Print: 2162-1969 First Step in Dissociation Process in the Gas Phase for Small Molecules with Neutral Atoms: Application with the Even-Odd Rule and a Specific Periodic Table for Organic and Inorganic Atoms Geoffroy Auvert Grenoble Alpes University, Grenoble, France How to cite this paper: Auvert, G. (2021) Abstract First Step in Dissociation Process in the Gas Phase for Small Molecules with Neutral Dissociations in the gas phase of small molecules have been intensively stu- Atoms: Application with the Even-Odd died and dissociation energies of various gases are available in reference Rule and a Specific Periodic Table for Or- works. Configurations of compounds before and after the dissociation are ganic and Inorganic Atoms. Open Journal of Physical Chemistry, 11, 54-63. usually known, but local charges are not defined. Building on the even-odd https://doi.org/10.4236/ojpc.2021.112003 rule, the topic of a series of previous articles by the same author, the objective of this paper is to show how it can be used to give electronic rules for dissoci- Received: March 17, 2021 Accepted: May 17, 2021 ations in gases. To this end, a specific periodic table is created and used. The Published: May 20, 2021 rules are applied to a selection of more than 30 common molecules, showing that the even-odd rule and its consequences are useful in explaining the phe- Copyright © 2021 by author(s) and nomenon of dissociation in gases. -
Catalytic Organic Transformations Mediated by Actinide Complexes
Inorganics 2015, 3, 392-428; doi:10.3390/inorganics3040392 OPEN ACCESS inorganics ISSN 2304-6740 www.mdpi.com/journal/inorganics Review Catalytic Organic Transformations Mediated by Actinide Complexes Isabell S. R. Karmel, Rami J. Batrice and Moris S. Eisen * Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Technion City, Haifa 32000, Israel; E-Mails: [email protected] (I.S.R.K.); [email protected] (R.J.B.) * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel./Fax: +972-4-829-2680. Academic Editors: Stephen Mansell and Steve Liddle Received: 16 September 2015 / Accepted: 9 October 2015 / Published: 30 October 2015 Abstract: This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field. Keywords: organoactinides; actinide coordination complexes; homogeneous catalysis; hydroelementations; polymerization of olefins; ROP; activation of heterocumulenes 1. Introduction The beginning of modern organoactinide chemistry is often attributed to the synthesis of 8 uranocene, [(η -C8H8)2U] in 1968, as the analogous compound to ferrocene and other transition metal metallocenes [1,2]. -
Open Dissertation Xiang Li 07032018.Pdf
The Pennsylvania State University The Graduate School Department of Chemistry MECHANOCHEMICAL SYNTHESIS OF CARBON AND CARBON NITRIDE NANOTHREAD SINGLE CRYSTALS A Dissertation in Chemistry by Xiang Li 2018 Xiang Li Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy August 2018 The dissertation of Xiang Li was reviewed and approved* by the following: John V. Badding Professor of Chemistry, Physics and Materials Science and Engineering Dissertation Advisor Chair of Committee Vincent H. Crespi Professor of Physics, Materials Science and Engineering, and Chemistry Paul S. Cremer Professor of Chemistry and Biochemistry and Molecular Biology Mauricio Terrones Professor of Physics, Chemistry and Materials Science and Engineering Thomas E. Mallouk Professor of Chemistry, Biochemistry and Molecular Biology, Physics, and Engineering Science and Mechanics Head of the Department of Chemistry *Signatures are on file in the Graduate School iii ABSTRACT Carbon nanomaterials such as fullerenes, nanotubes, and graphene have been widely studied in recent decades. Benefitting from their unique bonding, they possess extraordinary physical and chemical properties. Compared with sp2 hybridized carbon allotropes, there are significantly fewer new carbon materials dominated by sp3 bonding that have been developed. Adamantane and graphane represent the smallest unit and thinnest sheet of diamond possible, respectively. One-dimensional, mostly sp3 hybridized nanocarbon, did not yet exist in 2013, when the first synthesis of carbon nanothreads finally filled up the last remaining entry in the matrix of dimensionality and hybridization of carbon nanomaterials that year. Carbon nanothread was first made by compressing benzene to ~25 GPa in a large-volume anvil cell and slowly decompressing back to ambient pressure by an alumnus of the Badding group. -
Inorganic Chemistry for Dummies® Published by John Wiley & Sons, Inc
Inorganic Chemistry Inorganic Chemistry by Michael L. Matson and Alvin W. Orbaek Inorganic Chemistry For Dummies® Published by John Wiley & Sons, Inc. 111 River St. Hoboken, NJ 07030-5774 www.wiley.com Copyright © 2013 by John Wiley & Sons, Inc., Hoboken, New Jersey 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 Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permis- sion of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 646-8600. 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/permissions. Trademarks: Wiley, the Wiley logo, For Dummies, the Dummies Man logo, A Reference for the Rest of Us!, The Dummies Way, Dummies Daily, The Fun and Easy Way, Dummies.com, Making Everything Easier, and related trade dress are trademarks or registered trademarks of John Wiley & Sons, Inc. and/or its affiliates in the United States and other countries, and may not be used without written permission. All other trade- marks are the property of their respective owners. John Wiley & Sons, Inc., is not associated with any product or vendor mentioned in this book. -
Diphosphazide-Supported Trialkyl Thorium(IV) Complex Tara K
pubs.acs.org/Organometallics Communication Diphosphazide-Supported Trialkyl Thorium(IV) Complex Tara K. K. Dickie, Ashraf A. Aborawi, and Paul G. Hayes* Cite This: Organometallics 2020, 39, 2047−2052 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: The potassium salt of a new ligand, KLP=N3 (2, κ5 i i − LP=N3 = -2,5-[(4- PrC6H4)N3 P Pr2]2N(C4H2) ), that features two units of the rare phosphazide (RN3 PR3) functionality was synthesized via an incomplete Staudinger reaction between K[2,5- i i ( Pr2P)2N(C4H2)] (1)and4-PrC6H4N3. The diphosphazide ligand was transferred to a thorium(IV) metal center using salt metathesis strategies, yielding LP=N3ThCl3 (3), which contains two intact and coordinated phosphazides. Reaction of complex 3 with 3 equiv of LiCH2SiMe3 resulted in formation of the trialkyl thorium species LP=N3Th(CH2SiMe3)3 (4). In contrast, attempts to synthesize an organothorium complex supported by the previously κ3 reported bisphosphinimine ligand LP=N (LP=N = -2,5- i i − ff [(4- PrC6H4)N P Pr2]2N(C4H2) )aorded the cyclometalated * * κ4 i i i i 2− dialkyl complex L P=NTh(CH2SiMe3)2 (6,L PN = -2-[(4- PrC6H3)N P Pr2]-5-[(4- PrC6H4)N P Pr2]N(C4H2) ) and 1 equiv of free tetramethylsilane. 1 he Staudinger reaction, discovered in 1919, introduced the facile loss of N2, and, accordingly, were overlooked as ′ ’ T the formation of a phosphinimine group (R3P NR ) via viable functional groups in ligand design. Since Staudinger s the reaction of a tertiary phosphine (R3P) with an organic original work, multiple methods have been developed to ′ azide (N3R ), resulting in concomitant loss of N2. -
Summaries of FY 1997 Research in the Chemical Sciences
DOE/NBM-1098 Rev.-1 September 1997 T O EN FE TM N R E A R P G E Y D U • • A N C I I T R E D E M ST A ATES OF Summaries of FY 1997 Research in the Chemical Sciences U.S. Department of Energy Office of Energy Research Division of Chemical Sciences A searchable version of this summary book is available at the following web address: http://websrv.er.doe.gov/asp/search.asp This search tool is also accessible from the Chemical Sciences web page at: http://www.er.doe.gov/production/bes/chm/chmhome.html Available to DOE and DOE contractors from the Office of Scientific and Technical Information, P.O. Box 62, Oak Ridge, TN 37831; prices available from (423) 576-8401 Available to the public from the U.S. Department of Commerce, Technology Administration, National Technical Information Service, Springfield, VA 22161 This document was produced under contract number DE-AC05-76OR00033 between the U.S. Department of Energy and Oak Ridge Associated Universities. ORISE 97-1555 CONTENTS CONTENTS PREFACE ........................................................................ vii Oak Ridge National Laboratory.............................. 42 DIVISION OF CHEMICAL SCIENCES ..................... viii Pacific Northwest National Laboratory .................. 44 PROGRAM DESCRIPTIONS ........................................ ix Heavy Element Chemistry ....................................... 45 LABORATORY ADMINISTRATION ......................... xiii Argonne National Laboratory ................................. 45 Lawrence Berkeley National Laboratory............... -
Alkaline-Earth Metal Compounds Oddities and Applications 45 Topics in Organometallic Chemistry
Topics in Organometallic Chemistry 45 Sjoerd Harder Editor Alkaline-Earth Metal Compounds Oddities and Applications 45 Topics in Organometallic Chemistry Editorial Board: M. Beller l J. M. Brown l P. H. Dixneuf A. Fu¨rstner l L. J. Gooßen P. Hofmann l T. Ikariya l S. Nolan L. A. Oro l Q.-L. Zhou Topics in Organometallic Chemistry Recently Published Volumes Inventing Reactions Iridium Catalysis Volume Editor: Lukas J. Gooßen Volume Editor: P. G. Andersson Vol. 44, 2013 Vol. 34, 2011 Hydrofunctionalization Iron Catalysis – Fundamentals and Volume Editors: Valentine P. Ananikov, Applications Masato Tanaka Volume Editor: B. Plietker Vol. 43, 2013 Vol. 33, 2011 Organometallics as Catalysts Medicinal Organometallic Chemistry in the Fine Chemical Industry Volume Editors: G. Jaouen, N. Metzler-Nolte Volume Editors: Matthias Beller, Vol. 32, 2010 Hans-Ulrich Blaser C-X Bond Formation Vol. 42, 2012 Volume Editor: A. Vigalok Modern Organoaluminum Reagents: Vol. 31, 2010 Preparation, Structure, Reactivity and Use Transition Metal Complexes of Neutral Volume Editors: Simon Woodward, h1-Carbon Ligands Samuel Dagorne Volume Editors: R. Chauvin, Y. Canac Vol. 41, 2012 Vol. 30, 2010 Organometallic Pincer Chemistry Photophysics of Organometallics Volume Editors: Gerard van Koten, Volume Editor: A. J. Lees David Milstein Vol. 29, 2010 Vol. 40, 2012 Molecular Organometallic Materials Organometallics and Renewables for Optics Volume Editors: Michael A. R. Meier, Volume Editors: H. Le Bozec, V. Guerchais Bert M. Weckhuysen, Pieter C. A. Bruijnincx Vol. 28, 2010 Vol. 39, 2012 Conducting and Magnetic Organometallic Transition Metal Catalyzed Enantioselective Molecular Materials Allylic Substitution in Organic Synthesis Volume Editors: M. Fourmigue´, L. Ouahab Volume Editor: Uli Kazmaier Vol. -
Hayes, P. G. “Actinide Pincer Chemistry: a New Frontier”
Chapter 7 Actinide Pincer Chemistry: A New Frontier Connor S. MacNeil, Tara K.K. Dickie and Paul G. Hayes University of Lethbridge, Lethbridge, AB, Canada Chapter Outline 7.1 Introduction 133 7.3.5 Redox-Active Ligands 156 7.2 General Synthetic Strategies for Preparing 7.4 Catalytic Reactions Mediated by Actinide Actinide Pincer Complexes 135 Pincer Complexes 167 7.3 Synthesis, Structure, and Stoichiometric Reactivity 7.4.1 Hydroamination 167 of Actinide Pincer Complexes 136 7.4.2 Ring-Opening Polymerization 168 7.3.1 Neutral Ligands 136 7.4.3 Ethylene Polymerization 169 7.3.2 Monoanionic Ligands 137 7.5 Conclusion 169 7.3.3 Dianionic Ligands 142 Acknowledgments 169 7.3.4 Trianionic Ligands 156 References 170 7.1 INTRODUCTION Chemistry with actinide metals has historically been underdeveloped due to the inherent difficulties in handling molecu- lar actinide complexes. Actinide chemistry is generally only practiced with thorium and uranium for reasons of cost and availability, as well as radioactivity. While all the actinide elements are radioactive, thorium and uranium have α 1 . extremely long half-lives compared to most other metals in the actinide series. Thorium-232 is an -emitter with t/2 14 billion years. Depleted uranium is primarily U-238, which also emits an α-particle when it decays and has a half-life of more than 4 billion years. For these reasons, uranium and thorium are generally considered weakly radioactive [1,2]. Despite the associated complications, actinide chemistry is of great fundamental interest, and has thus blossomed into a rapidly emerging subfield of both inorganic and organometallic chemistry. -
Non-Donor Ligands in Organoactinide Chemistry
NON-DONOR LIGANDS IN ORGANOACTINIDE CHEMISTRY RIGID NON-DONOR PINCER LIGANDS IN ORGANOACTINIDE CHEMISTRY By NICHOLAS R. ANDREYCHUK, H.B.Sc A Thesis Submitted to the School of Graduate Studies in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy McMaster University © Copyright by Nicholas R. Andreychuk, March 2017. Ph.D. Thesis Nicholas R. Andreychuk Department of Chemistry and Chemical Biology McMaster University DOCTOR OF PHILOSOPHY (2017) McMaster University (CHEMISTRY) Hamilton, Ontario TITLE: Rigid NON-Donor Pincer Ligands in Organoactinide Chemistry AUTHOR: Nicholas R. Andreychuk SUPERVISOR: Prof. David J. H. Emslie NUMBER OF PAGES: xli, 312 ii Ph.D. Thesis Nicholas R. Andreychuk Department of Chemistry and Chemical Biology McMaster University Abridged Abstract The coordination- and organometallic chemistry of uranium complexes bearing the non-carbocyclic ancillary ligand XA2 (4,5-bis(2,6-diisopropylanilido)-2,7-di-tert- butyl-9,9-dimethylxanthene) has been developed as a major focus of this thesis. A number of air-sensitive actinide chloro complexes and alkyl derivatives featuring reactive An–C bonds were prepared, and investigated using a variety of structural and spectroscopic analytical techniques, including X-ray diffraction, NMR spectroscopy, elemental analysis, and electrochemical methods. The research described in this thesis serves to expand the currently underdeveloped, fundamental chemistry of actinide complexes supported by non-carbocyclic (i.e. non-cyclopentadienyl) ligands. For example, the use of the prototypical xanthene-based ligand XA2 has led to neutral dialkyl uranium(IV) complexes which a) react with alkyl anions to yield anionic trialkyl ‘ate’ complexes, b) C–H activate neutral pyridines to yield organouranium(IV) species featuring cyclometalated pyridine-based ligands, and c) react with Lewis acids to yield rare examples of cationic monoalkyl uranium(IV) complexes featuring coordinated arene ligands. -
The Chemical Complexities of Plutonium David L
The Chemical Complexities of Plutonium David L. Clark ew people have ever seen plutonium, and far fewer have actually handled or manipu- lated it. Yet this manmade element has arguably altered the course of civilization as Fmuch as copper, bronze, iron, or steel. Within five years of its synthesis, the primary use of plutonium was for the release of nuclear energy in weapons of mass destruction, and it seemed that the new element might lead the human race to the brink of self-annihilation. But instead, plutonium has become a stabilizing agent in global politics, forcing the human race to govern itself without resorting to nuclear war. Never before has a simple chemical element had such a profound impact on the consciousness of mankind. Plutonium has had a similarly humbling impact in the more circumscribed arena of science. Incredibly, it displays physicochemical behaviors that are among the most complex of any element in the periodic table. The pure element exhibits seven distinct crystal phases, is highly reactive, and is known to form compounds, complexes, or alloys with virtually every other element. Molten plutonium is highly corrosive and will slowly react with its container, causing difficulties for handling. When elemental plutonium reacts to give up its valence electrons, it can form a wide variety of positively charged ions with the ability to form up to twelve chemical bonds to other ions or molecules in solution. The element can exhibit five oxidation states, and under certain chemical conditions, four different oxidation states can be present in appreciable amounts simultaneously! No other element displays such a complex chemistry. -
Principles of Chemical Recognition and Transport in Extractive
2011 Separations and Heavy Element Chemistry Research Meeting Hyatt Regency, Baltimore, MD April 26 - 29, 2011 Office of Basic Energy Sciences Chemical Sciences, Geosciences & Biosciences Division Program and Abstracts for the 2011 Separations and Heavy Element Chemistry Research Meeting Hyatt Regency Baltimore, MD April 26–29, 2011 Chemical Sciences, Geosciences, and Biosciences Division Office of Basic Energy Sciences Office of Science U.S. Department of Energy i Cover Graphics: The cover artwork is used by permission from the authors and journals for the associated covers. These covers are related to recently published papers by PIs speaking in this meeting’s program. From left to right and top to bottom they are: Christopher Cahill on p. 19 of this book. Also see C. E. Rowland and C. L. Cahill (2010) "Capturing Hydrolysis Products in the Solid State: Effects of pH on Uranyl Squarates under Ambient Conditions." Inorganic Chemistry, 49(19), 8668–8673. Wibe A. de Jong on p. 77 of this book. Also see V.A. Glezakou and W.A. de Jong, "Cluster-models for Uranyl(VI) adsorption on α-alumina." J. Phys. Chem. A 2011, 115, 1257 (2011). Jaqueline Kiplinger on p. 9 of this book. Also see Thomson, R. K.; Graves, C. R.; Scott, B. L.; Kiplinger, J. L. “Noble Reactions for the Actinides: Safe Gold-Based Access to Organouranium and Azide Complexes,” Eur. J. Inorg. Chem. 2009, 1451–1455. Jaqueline Kiplinger on p. 9 of this book. Also see Cantat, T.; Graves, C. R.; Scott, B. L.; Kiplinger, J. L. “Challenging the Metallocene Dominance in Actinide Chemistry with a Soft PNP Pincer Ligand: New Uranium Structures and Reactivity Patterns,” Angew. -
Myersalexander.Pdf (3.037Mb)
SYNTHESIS AND REACTIVITY OF LOW-VALENT URANIUM AND NEPTUNIUM COMPLEXES _______________________________________ A Dissertation presented to the Faculty of the Graduate School at the University of Missouri-Columbia _______________________________________________________ In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy _____________________________________________________ By ALEXANDER J. MYERS Dr. Justin R. Walensky, Dissertation Supervisor DECEMBER 2019 The undersigned, appointed by the dean of the Graduate School, have examined the dissertation entitled SYNTHESIS AND REACTIVITY OF LOW-VALENT URANIUM AND NEPTUNIUM COMPLEXES presented by Alexander J. Myers, a candidate for the degree of Doctor of Philosophy of Chemistry, and hereby certify that, in their opinion, it is worthy of acceptance. Professor Justin R. Walensky Professor Silvia S. Jurisson Professor Wesley H. Bernskoetter Professor Bret D. Ulery Acknowledgements I would like to thank my wife, Heather Saxon, who encouraged me to go to graduate school in the first place. None of this would have happened if it wasn’t for you. My advisor, Justin Walensky, for all of his help, advice and the opportunities he has given me. I don’t know how you put up with me all these years but I’m glad you did. Wayne Lukens for all of his help; teaching me about preparing and running my SQUID and EPR samples. Charles Barnes, Steven Kelley, and Wei Wycoff, for their help with X-ray Crystallography and NMR spectroscopy Everyone in the Walensky group: Andrew Behrle, Pokpong Rungthanaphatsophon, Michael Tarlton, Robert Ward, Sean Vilanova, Alexander Gremillion, Andrew Lane, Andrew Breshears, Kira Behm, Matthew Vollmer, Steven Renfroe, and Jonathan Fajen. ii TABLE OF CONTENTS Acknowledgements .......................................................................................................