DOCSLIB.ORG

Cationic Complexes of the Group 13-15 Elements Supported by N-, P-, and O-Based Ligands

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Cationic Complexes of the Group 13-15 Elements Supported by N-, P-, and O-Based Ligands Cationic Complexes of the Group 13-15 Elements Supported by N-, P-, and O-based Ligands by Paul A. Gray B.ScH, Acadia University, 2012 A Dissertation Submitted in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY in the Department of Chemistry Paul A. Gray, 2018 University of Victoria All rights reserved. This dissertation may not be reproduced in whole or in part, by photocopy or other means, without the permission of the author. ii Supervisory Committee Cationic Complexes of the Group 13-15 Elements Supported by N-, P-, and O-based Ligands by Paul A. Gray B.ScH, Acadia University, 2012 Dr. Neil Burford, (Department of Chemistry) Supervisor Dr. Robin G. Hicks, (Department of Chemistry) Departmental Member Dr. David J. Berg, (Department of Chemistry) Departmental Member Dr. Jay T. Cullen, (Department of Earth and Ocean Sciences) Outside Member iii Abstract Supervisory Committee Dr. Neil Burford, (Department of Chemistry) Supervisor Dr. Robin G. Hicks, (Department of Chemistry) Departmental Member Dr. David J. Berg, (Department of Chemistry) Departmental Member Dr. Jay T. Cullen, (Department of Earth and Ocean Sciences) Outside Member This dissertation presents the synthesis and characterization of a variety of neutral and cationic complexes featuring Group 13-15 element centres stabilized by N-, P-, and O- based donors. Unique aluminum and gallium cationic complexes are obtained from equimolar reactions of the metal halide with the chelating alkyl phosphine dmpe. However, using the analogous amine donor tmeda, neutral adducts are preferred for aluminum as well as for GaCl3, while cations are obtained for GaBr3 and GaI3. New cations of Ge(II) and Sn(II) were also discovered, featuring the coordination of either bipyridine ligands or dmpe. Utilizing bipyridine led to the expected mono and dicationic chelate complexes, however, using dmpe led to the formation of unprecedented tetracationic molecules. The reactivities of the bipyridine complexes were investigated with a variety of substrates which showcased their Lewis acidity as well as their ability to be oxidized. Finally, a new series of high oxidation-state main group cations have been synthesized using a variety of ligands. The ligand choice was found to be an important role iv in compound isolation as ligand degradation occurred for some of the compounds due to their high electrophilicity. Additionally, the Lewis acidity of some of the complexes leads to interesting reaction chemistry including sp3 C-H activation. Overall, the results presented herein represent new coordination chemistry for the main group elements and opens the door towards new reactivity pathways including small molecule activation and catalysis. v Table of Contents Supervisory Committee ........................................................................................................ ii Abstract ................................................................................................................................ iii Table of Contents .................................................................................................................. v List of Tables ..................................................................................................................... xiii List of Figures .................................................................................................................... viii List of Schemes .................................................................................................................... xi Chapter 1 - Introduction ........................................................................................................ 1 1.1 Renaissance of Main Group Chemistry .................................................................... 1 1.2 Approaches to Stabilizing Reactive Main Group Centres ........................................ 2 1.2.1 Effects of Sterically Demanding Substituents .................................................. 3 1.2.2 Coordinative Stabilization from Strong Donor Molecules ............................... 7 1.3 Reactivity of Unsaturated Heavy C=C and C≡C Analogues .................................. 10 1.4 Lewis Acid-Base Chemistry ................................................................................... 15 1.4.1 Traditional Lewis Acid-Base .......................................................................... 15 1.5 Frustrated Lewis Pairs............................................................................................. 16 1.6 Bonding Considerations in Donor-Acceptor Main Group Complexes ................... 19 1.7 Synthetic Methodologies ........................................................................................ 21 1.8 Scope of Thesis ....................................................................................................... 23 Chapter 2 - Amine and Phosphine Complexes of Aluminum and Gallium Halides .......... 25 2.1 Introduction ............................................................................................................. 25 2.2 Cationic Phosphine Complexes of Aluminum ........................................................ 27 2.3 Cationic Phosphine Complexes of Gallium ............................................................ 33 2.4 Structural Alternatives to Cationic Molecules ........................................................ 41 2.5 Amine Complexes of Aluminum and Gallium Halides .......................................... 44 2.6 Summary ................................................................................................................. 49 Chapter 3 - Donor-Acceptor Complexes of Ge(II) and Sn(II) Cations .............................. 51 3.1 - Cationic 2,2’-Bipyridine Complexes of Ge(II) and Sn(II) ................................... 53 3.2 Cationic Phosphine complexes of Ge(II) and Sn(II) ............................................... 63 3.3 Summary ................................................................................................................. 72 Chapter 4 - Reactivity of Cationic Ge(II) and Sn(II) Bipyridine Complexes ..................... 74 4.1 Assessing the Lone Pair Reactivity in Ge and Sn Dications ...................................... 78 4.2 Lewis Acid Behaviour of Ge(II) and Sn(II) Dications ........................................... 84 4.3 Reaction of a Ge(II) Dication with Water............................................................... 87 4.4 Attempted Oxidation of Ge(II) and Sn(II) Dications .............................................. 90 4.5 Summary ................................................................................................................. 93 Chapter 5 - Complexes of High Oxidation-State Main Group Cations .............................. 95 5.1 Preparation of an Octahedral Gallium Tricationic Complex .................................. 99 vi 5.2 Targeting Tricationic Aluminum Complexes ....................................................... 102 5.3 Synthesis of Highly-Charged Group 14 E(IV) Complexes .................................. 107 5.4 Attempted Synthesis of P(V) Pentacationic Complexes ....................................... 115 5.5 Summary ............................................................................................................... 119 Chapter 6 – Summary ....................................................................................................... 122 Chapter 7 – Future Work .................................................................................................. 126 7.1 New Ligands in Transition Metal Catalysis .......................................................... 126 7.2 C-F Bond Activation by Main Group Cations ...................................................... 127 Chapter 8 – Experimental ................................................................................................. 129 8.1 General Procedures ............................................................................................... 129 8.2 Compounds in Chapter 2 ...................................................................................... 131 8.2.1 Synthesis of [(dmpe)2AlCl2][AlCl4] ............................................................. 131 8.2.2 Synthesis of [(dmpe)2AlBr2][AlBr4] ............................................................. 132 8.2.3 Synthesis of [(dmpe)2AlI2][AlI4] .................................................................. 132 8.2.4 Synthesis of [(dmpe)2GaCl2][GaCl4] ............................................................ 133 8.2.5 Synthesis of [(dmpe)2GaBr2][GaBr4] ............................................................ 134 8.2.6 Synthesis of [(dmpe)2GaI2][GaI4] ................................................................. 134 8.2.7 Synthesis of (tmeda)AlCl3 ............................................................................ 135 8.2.8 Synthesis of (tmeda)AlBr3 ............................................................................ 135 8.2.9 Synthesis of (tmeda)AlI3 ............................................................................... 136 8.2.10 Synthesis of (tmeda)GaCl3 ........................................................................ 136 8.2.11 Synthesis of [(tmeda)GaBr2][GaBr4] ........................................................ 137 8.2.12 Synthesis of [(tmeda)GaI2][GaI4] ............................................................. 137 8.3 Compounds in Chapter 3 .....................................................................................
Load more

Recommended publications
  • 1 Introduction
    Phosphine-catalysed reductive coupling of Dihalophosphanes Jan-Erik Siewert,[a] André Schumann[a] and Christian Hering-Junghans*[a] [a] M.Sc. Jan-Erik Siewert, Dr. André Schumann, Dr. Chirstian Hering-Junghans Leibniz Institute of Catalysis e.V. Rostock (LIKAT) Albert-Einstein-Straße 29a, 18059 Rostock, Germany E-Mail: [email protected] Abstract Classically, tetraorgano diphosphanes have been synthesized through Wurtz-type reductive coupling of halophosphanes R2PX or more recently, through the dehydrocoupling of phosphines R2PH. Catalytic variants of the dehydrocoupling reaction have been reported but are limited to R2PH compounds. Using PEt3 as a catalyst, we now show that TipPBr2 (Tip = 2,4,6-iPr3C6H2) is selectively coupled to give the dibromodiphosphane (TipPBr)2 (1), a compound not accessible using classic Mg reduction. Surprisingly, when using DipPBr2 (Dip = 2,6-iPr3C6H3) in the PEt3-catalysed reductive coupling the diphosphene (PDip) 2 (2) with a P=P double was formed selectively. In benzene solutions (PDip)2 has a half life-time of ca. 28 days and can be utilized with NHCs to access NHC-phosphinidene adducts. Control experiments show that [BrPEt3]Br is a potential oxidation product in the catalytic cycle, which can be then debrominated by using Zn dust as sacrificial reductant. 1 Introduction The formation of element-element bonds in main group chemistry is still dominated by classic stoichiometric salt metathesis and reductive coupling reactions. Only in S1 recent years, catalytic protocols for the dehydrocoupling of main group (p-block) substrates to species with homonuclear (E−E) or heteronuclear (E−E’) bonds have emerged.1-3 Catalysis with earth-abundant metals, in particular Zr, Fe and Ni,4 has been shown to be a viable alternative to using rather expensive systems based on Rh,5-7 Ir7- 10 and Ru.11 Using main-group species to facilitate the homo- or heterocoupling of p- block elements has also been in the focus of current research.
    [Show full text]
  • Status of Inorganic Chemistry Research in India
    Proc Indian Natn Sci Acad 86 No. 2 June 2020 pp. 983-999 Printed in India. DOI: 10.16943/ptinsa/2019/49735 Review Article Status of Inorganic Chemistry Research in India V CHANDRASEKHAR1,2,* and A CHAKRABORTY2 1Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016, India 2Tata Institute of Fundamental Research Hyderabad, Gopanpally, Hyderabad 500 107, India (Received on 03 March 2019; Revised on 25 May 2019; Accepted on 05 June 2019) The current status of research in the area of Inorganic chemistry in India is discussed. The article focuses on various aspects of inorganic chemistry being pursued in the country such as main-group chemistry, coordination chemistry, supramolecular chemistry, molecular materials and bio-inorganic chemistry. The strengths of the subject in the country and the possible future directions are discussed. Keywords: Inorganic Chemistry; Modern Chemistry; Chemical Research; Mercurous Nitrite Introduction for a long time and the amount of funding was substantially lower. It is only in the last two decades Modern chemistry research in India began with that reasonable funding became available for Acharya Prafulla Chandra Ray in Kolkata. The fact researchers across the country and this is reflected that he was an inorganic chemist by training is in the number of publications resulting from the incidental. His influence on chemical research in India country. The increased funding has resulted in higher is profound (Chakravorty, 2014). His most important number of publications. By a search of web-of-science contribution is the preparation of mercurous nitrite, using the key words “India” and “Address” (in topics Hg (NO ) , whose molecular structure was 2 2 2 search) the publications in the decades 1980-2019 is established several years later (Samanta et al., 2011).
    [Show full text]
  • Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005)
    NOMENCLATURE OF INORGANIC CHEMISTRY IUPAC Recommendations 2005 IUPAC Periodic Table of the Elements 118 1 2 21314151617 H He 3 4 5 6 7 8 9 10 Li Be B C N O F Ne 11 12 13 14 15 16 17 18 3456 78910 11 12 Na Mg Al Si P S Cl Ar 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 55 56 * 57− 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 Cs Ba lanthanoids Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 87 88 ‡ 89− 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 Fr Ra actinoids Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uus Uuo * 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu ‡ 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr International Union of Pure and Applied Chemistry Nomenclature of Inorganic Chemistry IUPAC RECOMMENDATIONS 2005 Issued by the Division of Chemical Nomenclature and Structure Representation in collaboration with the Division of Inorganic Chemistry Prepared for publication by Neil G.
    [Show full text]
  • Lawrence Berkeley National Laboratory Recent Work
    Lawrence Berkeley National Laboratory Recent Work Title REFERENCES TO ULTRAVIOLET PHOTOELECTRON SPECTRA OF GASEOUS MOLECULES Permalink https://escholarship.org/uc/item/3bf9869z Authors Horne, D.H. Jolly, W.L. Publication Date 1986-09-01 eScholarship.org Powered by the California Digital Library University of California DISCLAIMER This document was prepared as an account of work sponsored by the United States Government. While this document is believed to contain COlTect information, neither the United States Government nor any agency thereof, nor the Regents of the University of California, nor any of their employees, makes any walTanty, express or implied, or assumes any legal responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, proCess, or service by its trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof, or the Regents of the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof or the Regents of the University of California. , References to Ultraviolet Photoelectron Spectra of Gaseous Molecules By Dorothy H. Horne and William L. Jolly Materials and Molecular Research Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720 This report consists of an alphabetical listing of compounds together with Chemical Abstracts references (for the years 1972-1985) to articles describing research in which these compounds are the subject of gas-phase ultraviolet photoelectron spectroscopic studies.
    [Show full text]
  • From the Activation of Tetraphosphorus to the Chemistry
    From the Activation of Tetraphosphorus to the Chemistry of Diphosphorus and Beyond by Daniel Tofan B.S., California Institute of Technology (2008) Submitted to the Department of Chemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY June 2013 © Massachusetts Institute of Technology 2013. All rights reserved. Author.......................................................................... Department of Chemistry May 28, 2013 Certified by. Christopher C. Cummins Professor of Chemistry Thesis Supervisor Accepted by . Robert W. Field Chairman, Department Committee on Graduate Theses 2 This Doctoral Thesis has been examined by a Committee of the Department of Chemistry as follows: Professor Mircea Dinca..................................................................˘ Assistant Professor of Chemistry Chairman Professor Christopher C. Cummins . Professor of Chemistry Thesis Supervisor Professor Elizabeth M. Nolan . Pfizer Laubach Career Development Assistant Professor of Chemistry Committee Member 3 4 From the Activation of Tetraphosphorus to the Chemistry of Diphosphorus and Beyond by Daniel Tofan Submitted to the Department of Chemistry on May 28, 2013, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Abstract − t The niobium–phosphorus triple bond in [P≡Nb(N[Np]Ar)3] (Np = CH2 Bu; Ar = 3,5-Me2C6H3) has produced the first case of P4 activation by a metal–ligand multiple bond. Treatment of P4 with the sodium salt of the niobium phosphide complex in weakly-coordinating solvents led to the for- mation of the C3-symmetric cyclo-P3 anion, while in THF, it led to the formation of the cyclo-P5 4 − anion [(Ar[Np]N)(h -P5)Nb(N[Np]Ar)2] .
    [Show full text]
  • Program and Abstracts
    Program and Abstracts 8-11 December, 2015 The University of Sydney Sydney, AUSTRALIA SPONSORS WELCOME TO OZOM IX Welcome to OZOM IX, the 9th Australasian Organometallics meeting of the Royal Australian Chemical Institute, focussing on the cross-divisional discipline of organometallic chemistry. The program again caters for all applications of the field. In keeping with the common theme of all the previous highly successful meetings in this series, the program also maintains its strong student and early career researcher focus through both contributed oral and poster presentations. In addition, a number of eminent researchers from Germany will be delivering plenary lectures at the meeting amongst a further list of international delegates attending the meeting. The organising committees would like to extend a warm welcome to all delegates. Enjoy your time in Sydney! Local Organising Committee Lou Rendina (Chair) Rob Baker (Treasurer) Peter Lay Tony Masters Peter Rutledge Ant Ward National Organising Committee Phil Andrews, Marie Cifuentes, Michael Gardiner, Mark Humphrey, Peter Junk, and George Koutsantonis DETAILED PROGRAM TUESDAY 8 DECEMBER 17.30 - 18.30 Registration (The Grandstand) 18.30 - 20.30 Opening Mixer (The Grandstand) WEDNESDAY 9 DECEMBER 8.50 - 9.00 Welcome (Lou Rendina, Chair) 9.00 - 10.00 Plenary Lecture 1 (PL1): Prof. F. E. Hahn LECTURE SESSION Synthesis and Reactivity of Complexes Bearing Protic NHC Session Chair: Ligands George Koutsantonis 10.00 - 10.20 Oral Lecture 1 (OL1): N. Camasso Design, Synthesis, and Reactivity of Organometallic Ni(IV) Complexes 10.20 - 10.40 Oral Lecture 2 (OL2): S. Scottwell The Synthesis and Switching of a Molecular Folding Ruler 10.40 - 11.10 morning tea LECTURE SESSION 11.10 - 11.30 Oral Lecture 3 (OL3): S.
    [Show full text]
  • NBO Applications, 2012
    NBO 2012 (Jan-Dec) – 1287 references Updated 4/3/2013 – Ariel Neff Abdel-Ghani, N. T.; Mansour, A. M. Molecular structures of antitumor active Pd(II) and Pt(II) complexes of N,N-donor benzimidazole methyl ester Journal of Coordination Chemistry, (65): 763-779 2012. Abdel-Rhman, M. H.; Hassanian, M. M.; El-Asmy, A. A. Spectral and structural density functional theory on 4-ethyl and 4-(p-tolyl)-1-(pyridin-2- yl)thiosemicarbazides and their Pd(II) complexes Journal of Molecular Structure, (1019): 110-119 2012. Acharjee, N.; Banerji, A.; Prange, T. Remarkable influence of mild Lewis acid catalysts on cycloadditions leading to tetrasubstituted isoxazolidines: DFT analysis augmented by X-ray and NMR studies Monatshefte fur Chemie, (143): 1687-1703 2012. Acosta-Silva, C.; Bertran, J.; Branchadell, V.; Oliva, A. Quantum-Mechanical Study on the Mechanism of Peptide Bond Formation in the Ribosome Journal of the American Chemical Society, (134): 5817-5831 2012. Adhikari, K.; Ray, A. K. Stabilities of silicon carbide nanocones: a nanocluster-based study Journal of Nanoparticle Research, (14) 2012. Adhikari, U.; Scheiner, S. Contributions of Various Noncovalent Bonds to the Interaction between an Amide and S- Containing Molecules Chemphyschem, (13): 3535-3541 2012. Adhikari, U.; Scheiner, S. Effects of carbon chain substituents on the P center dot center dot center dot N noncovalent bond Chemical Physics Letters, (536): 30-33 2012. Adhikari, U.; Scheiner, S. Substituent Effects on Cl center dot center dot center dot N, S center dot center dot center dot N, and P center dot center dot center dot N Noncovalent Bonds Journal of Physical Chemistry A, (116): 3487-3497 2012.
    [Show full text]
  • Curriculum Vitae Dr
    Curriculum Vitae Dr. David A. Dixon Robert Ramsay Chair Department of Chemistry The University of Alabama Birth Date Dec. 3, 1949 in Houston, Texas Address Department of Chemistry The University of Alabama 113 Shelby Hall Box 870336 Tuscaloosa, AL 35487-0336 Contact information Phone: 205-348-8441 Fax: 205-348-4704 eMail: [email protected] Education B.S. with honors, Chemistry, California Institute of Technology, Pasadena, California, June 1971 Ph.D., Physical Chemistry, Harvard University, Cambridge, Massachusetts, completed June 1975 (received March 1976) Thesis Supervisors: Professors D.R. Herschbach and W.N. Lipscomb Thesis Title: I. Reactions of van der Waals Molecules. II. Localized Molecule Orbitals for Polyatomic Molecules Positions Held Junior Fellow, Society of Fellows, Harvard University, Cambridge, Massachusetts, 7/1975 - 6/1977. Visiting Associate, Chemistry, California Institute of Technology, Pasadena, California, 2/1977 - 6/1977. Assistant Professor, Chemistry Department, University of Minnesota, Minneapolis, Minnesota, 9/1977 - 6/1983. Member of Research Staff, Chemical Sciences, Central Research and Development Department, E.I. du Pont de Nemours and Co., Inc. Wilmington, Delaware, 7/1983 -9/1995 Research Leader, computational chemistry, Central Research and Development, E. I. du Pont de Nemours and Co., Inc., Wilmington, Delaware, 1990 - 9/1995. Research Fellow, DuPont Central Science and Engineering Laboratories, Experimental Station, Wilmington, Delaware, 1992 - 9/1995 Associate Director, Theory, Modeling & Simulation, Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, 9/1995- 9/2002 1 Battelle Fellow, Pacific Northwest National Laboratory, 10/2002 – 12/2003 Professor of Chemistry, University of Alabama – Tuscaloosa, 1/2004 – Robert Ramsay Chair, Department of Chemistry, University of Alabama – Tuscaloosa, April, 2004 – Interim Chair, Department of Chemistry, University of Alabama – Tuscaloosa, Aug., 2007- Aug.
    [Show full text]
  • Nothing but Motion Other Books by Dewey B
    NOTHING BUT MOTION OTHER BOOKS BY DEWEY B. LARSON Physical Science The Structure of the Physical Universe The Case Against the Nuclear Atom Beyond Newton New Light on Space and Time Quasars and Pulsars Economic Science The Road to Full Employment NOTHING BUT MOTION Volume I of a revised and enlarged edition of THE STRUCTURE OF THE PHYSICAL UNIVERSE By DEWEY B. LARSON NORTH PACIFIC PUBLISHERS P. O. Box 13255 Portland, Oregon 97213 Copyright © 1959, 1965, 1979 By Dewey B. Larson All rights reserved Library of Congress Catalog Card No. 79-88078 ISBN 0-913138-07-x Contents Preface vii 1 Background 1 2 A Universe of Motion 15 3 Reference Systems 29 4 Radiation 43 5 Gravitation 57 6 The Reciprocal Relation 71 7 High Speed Motion 83 8 Motion in Time 97 9 Rotational Combinations 115 10 Atoms 127 11 Sub-atomic Particles 139 12 Basic Mathematical Relations 147 13 Physical Consta nts 157 14 Cosmic Elements 173 15 Cosmic Ray Decay 185 16 Cosmic Atom Building 199 17 Some Speculations 211 18 Simple Compounds 219 19 Complex Compounds 235 20 Chain Compounds 249 21 Ring Compounds 269 References 285 Index 289 v Preface Nearly twenty years have passed since the first edition of this work was published. As I pointed out in the preface of that first edition, my findings indicate the necessity for a drastic change in the accepted concept of the fundamental relationship that underlies the whole structure of physical theory: the relation between space and time. The physical universe, I find, is not a universe of matter existing in a framework provided by space and time, as seen by conventional science, but a universe of motion, in which space and time are simply the two reciprocal aspects of motion, and have no other significance.
    [Show full text]