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Durham E-Theses Studies in the coordination chemistry of some main group metals and metalloids Bryan, Stephen James How to cite: Bryan, Stephen James (1983) Studies in the coordination chemistry of some main group metals and metalloids, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/9320/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk 2 The copyright of this thesis rests with the author. No quotation from it should be published without his prior written consent and information derived from it should be acknowledged. STUDIES IN THE COORDINATION CHEMISTRY OF SOME MAIN GROUP METALS AND METALLOIDS by STEPHEN JAMES BRYAN B.Sc. (Hatfield College) A thesis submitted for the degree of Doctor of Philosophy in the University of Durham. Department of Chemistry September 1983. 25.«fM To my parents. The copyright of this thesis rests with the author. No quotation from it should be published without his prior written consent and information derived from it should be acknowledged. CONTENTS Page Acknowledgements i Memorandum ii Abstract iii PART 1 METHYLENEAMINO DERIVATIVES OF SOME MAIN GROUP METALS AND METALLOIDS"! CHAPTER 1 BONDING MODES OF SOME METHYLENEAMINO LIGANDS 1 CHAPTER 2 PREPARATION AND CHARACTER!SATION OF SOME ASSOCIATED METHYLENEAMINOBORANES AND RELATED STUDIES Introduction 11 Experimental Section (i) Preparation of BMe3 11 (ii) Preparation of BEtg 12 (iii) Preparation of B2H^ 13 (iv) Preparation of Me2BH2BMe2 13 (v) Reaction of CH3CN and Me2BH2BMe2 (2:1) 14 vi 15 ( -) Reaction of CH3CH2CN and Me2BH2BMe2 ( 2 :1) t (vii) Reaction of BuCN and Me2BH2BMe2 (2:1) 17 (viii) Reaction of PhCN and Me2BH2BMe2 (2:1) 17 (ix) Attempted reaction of (PhCH=NBMe9)0 and z BC13 * 18 (x) Reaction of CH2=CHCN and Me2BH2BMe2 (2:1) 19 (xi) Reaction of CH2=CHCN and Me2BH2BMe2 (1:1) 20 (xii) Reaction of CH2=CHCH2CN and Me2BH2BMe2 (2:1)20 t (xiii) Reaction of BuCN and BEt3 (1:1) 21 Page (xiv) Reaction of PhCN and BEtg (1:1) 22 (xv) Reaction of Me-jSiCN and Me2BH2BMe2 (2:1) 23 (xvi) Reaction of Me3SiCN and Me2BCl (1:1) . 24 (xvii) Reaction of Me2BCN and Me2BH2BMe2 (2:1) 24 DISCUSSION 26 CHAPTER 3 REACTIONS OF LITHIUM TRIETHYLBOROHYDRIDE WITH SOME NlTRlLES; THE REACTIVITY OF LITHIUM t-BUTYL-, AND PHENYL-, METHYLENEAMINOTRIETHYLBORATE TOWARDS PHOSPHORUS TRICHLORIDEI Introduction 60 Experimental Section (i) Starting materials 60 (ii) Reaction of LiBHEt^ and CH-jCN (1:1) 60 (iii) Reaction of LiBHEtg and CH3CN (2:1) 61 (iv) Reaction of LiBHEt^ and tBuCN (1:1) 62 (v) Reaction of LiBHEt., PMDETA and CBuCN (1:1:1) J 62 t (vi) Attempted reaction of BEt^ and Bu2C=NLi 63 (vii) Reaction of LiBHEt3 and PhCN(l:l) 64 (viii) Formation of Li(TMED)2BHEt3 65 (ix) Reaction of Li(TMED)2BHEt3 and PhCN (1:1) 65 (x) Proce dure for chromatographic examination of reaction products 66 t (xi) Reaction of BuCH=N(BEt3)Li and PC13 (1:1) 66 (xii) Reaction of PhCH=N(BEt3)Li and PC13 67 (xiii) Reactions of tBuCH=N(BEt^)Li and J PhCH=N(BEt3)Li with PC13 (2:1) 68 (xiv) Reaction of tBuCH=N(BEto)Li and J PC13 (3:1) 68 (xv) Reaction of PhCH=N(BEto)Li and J PC13 (3:1) 69 Discussion 71 Page CHAPTER 4 SOME MONOMERIC DI-t-BUTYLMETHYLENEAMINO DERIVATIVES OF BORON Introduction 102 Experimental Section (i) Starting materials 102 t (ii) Preparation of Bu2C=NBCl2 103 t ( i i i ) Preparation of Bu2C^NBMe2 10'} t (iv) Reaction of Bu2C=NH and Me2BH2 BMe 2(2:1) 105 t (v) Preparation of Bu2C=NBPh2 105 (vi) Preparation of C12HgBF 106 t (vii) Preparation of Bu2C=NB(C12Hg) 106 t (viii) Preparation of ( Bu2C=N)2BF 107 t (ix) Preparation of ( Bu2C=N)3B 108 t (x) Reaction of Bu2C=NLi and BF3.0Et2 (4:1) 109 t (xi) Attempted reaction of ( Bu?C=N) 3B and LiBHEt3 109 t (xii) Attempted reaction of ( Bu9C-^N) 3B and MeLi ^ 110 t (xiii) Attempted reaction of ( Bu9C=N) 3B and z CH3CN 110 t (xiv) Preparation of Bu2C=NH2BF^ 110 Discussion 112 Appendix Crystal structure of Bu^NH^BF^ 144 CHAPTER 5 SOME METHYLENEAMINO DERIVATIVES OF ALUMINIUM Inlroduct i on I 50 Page Experimental Section (i) Starting materials 150 (ii) Reaction of Ph2C=NLiand A1C13 (1:1) 151 (iii) Reaction of Ph2C=NLi and A1C13 (2:1) (Reaction performed by Mr. B. Hall) 151 (iv) Reaction of Ph2C=NSiMe3 and AICI3 (3:1) 152 t (v) Reaction of Bu2C=NSiMe3 and A1C13 (3:1) 153 t (vi) Reactions of Ph2C=NSiMe3 and Bu2C=NSiMe3 with A1C13 in tne absence of solvent 153 (vii) Reaction of Ph2C=NLi and A1C13 (4:1) 154 (viii) Reaction of Ph2C=NLi and Me2AlCl (2:1) 154 (ix) Reaction of (C12Hg)C=NSiMe3 and A1C13 155 Discussion 158 CHAPTER 15N n.m.r. SPECTRA OF SOME METHYLENEAMINES AND METHYLENEAMINO DERIVATIVES" Introduction 189 Experimental Section (i) Preparation of previously reported compounds 189 C (ii) Preparation of ( Bu2C=N)3P 190 15 (iii) Procedure for obtaining N n.m.r. spectra 191 Discussion 193 Page PART 2 STUDIES IN THE METAL-DERIVATIVE CHEMISTRY OF SOME BOKANES AND CARBORANES CHAPTER 7 SOME METAL DERIVATIVES OF ICOSAHEDRAL CARBORANES CONTAINING METAL-CARBON <r, BONDS Introduction 203 Experimental Section (i) Starting materials 206 (ii) Preparation of Li C2B10H10Me 206 (iii) Preparation of Li (C2B1()H10Me) (PMDETA) 207 (iv) Addition of PMDETA to LiC2B10H1;L 208 (v) Addition of TMEDA to Li C2B10H1;L 208 (vi) Preparation of C2B10H1()MeBr 209 (vii) Preparation of Mg(C0B1nH1 nMe)9 1 10 10 1 (C4Hg02)2.C7H8 209 (viii) Reaction of LiC0B1 .-.H-,n Me and MeAlCl9 (2:1) 210 (ix) Reaction of LiC2B1()H10Me and Me2AlCl(l:l) 211 Discussion 212 CHAPTER 8 ATTEMPTS AT THE PREPARATION OF SOME ICOSAHEDRAL- closo-DI C0BALTAB0RANES : : Introduction 236 Experimental Section . 236 Discussion 236 APPENDIX 1 GENERAL EXPERIMENTAL TECHNIQUES 248 APPENDIX 2 RESEARCH COLLOQUIA, SEMINARS, LECTURES "CONFERENCES T980-1983. " 2r>2 RKKKRKNCKS 2f>4 - i - ACKNOWLEDGEMENTS I should like to express my thanks to Professor K. Wade, under whose supervision this work was performed, for his encouragement and invaluable advice. A number of other people have also provided considerable assistance during the course of this work. Five of the six crystal structures described here for the first time were determined by Dr. W. Clegg of the Institut fur Anorganische Chemie der Universitat, Gottingen, Federal Republic of Germany. The remaining structure was determined by Dr. J. Halfpenny, formerly of this University, ;ind currently of Napier College, Edinburgh. The' ' 'N n.m.r. spectra were recorded by Dr. M.W. Cooper of PCMU, Harwell as part of a collaborative study with Dr. J. Mason of the Open University. I am grateful to Dr. R. Snaith and co-workers of Strathclyde University for the provision of some of the samples used in this ^~*N n.m.r. study, and additionally to Dr. Snaith for the provision of the unpublished bond index data discussed in Chapter 4. Mr. B. Hall, of these laboratories, has provided occasional, though valuable, technical assistance, and I am grateful, to Mrs. M. Chipchase for typing the text of this thesis. Finally, the provision of a Science and Engineering Research Council maintenance grant is gratefully acknowledged. S.J. Bryan. ii MEMORANDUM The work described in this thesis was carried out in the University of Durham between September 1980 and September 1983. It has not been submitted for any other degree, and is the original work of the author except where acknowledged by reference. Some aspects of this work have formed the basis of the following publications : 'Preparation and X-Ray crystal structures of the dimeric- anc aldiminoborane (PhCH=NBMe2)2 * monomeric paddle-wheel t shaped tris(ketimino)borane B(N=C Bu2)3', by J. Robert Jennings, Ronald Snaith, Muayyad M. Mahmoud, Stephen C. Wallwork, Stephen J. Bryan, Joan Halfpenny, Elizabeth A. Petch and Kenneth Wade, J. Organomet Chem., 1983, 249, CI. 'Crystal Structure of the pentamethyldiethylenetriamine adduct of l-Lithio-2-methyl-l,2-dicarba-closo-dodecaborane, Li(C2B10H10Me)(MeN(CH2CH2NMe2)), a compound containing a lithium atom terminally bonded to a six coordinate carbon atom', by William Clegg, David A. Brown, Stephen J. Bryan and Kenneth Wade, Polyhedron, in press. During the course of his postgraduate study the author also contributed to the following publication : 'The Coordination chemistry of Acrylonitrile', by S.J. Bryan, P.G. Huggett, K. Wade, J.A. Daniels and J.R. Jennings, Coord. Chem. Rev., 1982, 44, 149. iii 'Studies in the coordination chemistry of some main group metals and metalloias1 by S. J. Bryan B.Sc. ABSTRACT Part I of this thesis describes the preparation of 1 2 some compounds containing methyleneamino ligands, R R C=N- attached to lithium, boron, aluminium and phosphorus. The compounds were synthesised with the aim of providing detailed information on the structural and spectroscopic consequences of methyleneamino-ligand bonding to both valence-saturated, and unsaturated, metals and metalloids.
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    INBO009 - BORAZINE BORAZINE Safety Data Sheet INBO009 Issue date: 05/01/2015 Revision date: 25/03/2021 Version: 2.2 SECTION 1: Identification of the substance/mixture and of the company/undertaking 1.1. Product identifier Product form : Substance Physical state : Liquid Substance name : BORAZINE Product code : INBO009 Formula : H6B3N3 Synonyms : TRIAZATRIBORINANE Chemical family : BORON COMPOUND 1.2. Relevant identified uses of the substance or mixture and uses advised against 1.2.1. Relevant identified uses Use of the substance/mixture : Chemical intermediate 1.2.2. Uses advised against No additional information available 1.3. Details of the supplier of the safety data sheet GELEST, INC. 11 East Steel Road Morrisville, PA 19067 USA T 215-547-1015 - F 215-547-2484 - (M-F): 8:00 AM - 5:30 PM EST [email protected] - www.gelest.com GELEST INC. Fritz-Klatte-Strasse 8 65933 Frankfurt Germany T +49 (0) 69 3535106-500 - F +49 (0) 69 3535106-501 - (M-F): 8:00 AM - 4:00 PM [email protected] - www.gelestde.com 1.4. Emergency telephone number Emergency number : CHEMTREC: 1-800-424-9300 (USA); +1 703-527-3887 (International) SECTION 2: Hazards identification 2.1. Classification of the substance or mixture Classification according to Regulation (EC) No. 1272/2008 [CLP] Flammable liquids, Category 2 H225 Skin corrosion/irritation, Category 1, Sub-Category 1B H314 Serious eye damage/eye irritation, Category 1 H318 Specific target organ toxicity — Single exposure, Category 3, H335 Respiratory tract irritation Full text of H statements : see section 16 Adverse physicochemical, human health and environmental effects No additional information available 2.2.
  • Reduction of Borazines Mediated by Lowvalent Chromium Species

    Reduction of Borazines Mediated by Lowvalent Chromium Species

    Angewandte. Communications DOI: 10.1002/anie.201206668 Chemical Hydrogen Storage Reduction of Borazines Mediated by Low-Valent Chromium Species** Tyler J. Carter, Jeff W. Kampf, and Nathaniel K. Szymczak* The past decade has seen significant effort focused on [1] developing high-capacity H2 storage materials. Low-molec- ular-weight B-N materials, such as ammonia–borane (NH3BH3 ; AB) have received particular attention because of their exceptionally high gravimetric density (19.6 wt%) for [2] chemical H2 storage. While the dehydrogenation of B-N [3] materials to afford H2 has been highly studied, the low- energy regeneration of spent B-N fuels has received less [4] Scheme 1. Dehydrogenation of B-N materials for hydrogen storage, attention and remains a coveted goal that needs to be and the subsequent rehydrogenation strategy under investigation. addressed before B-N compounds can be utilized as hydrogen storage materials. However, the direct hydrogenation of spent B-N fuels with H2 suffers from significant thermodynamic strategy that could in principle proceed through low-energy constraints, as revealed by experimental and computational pathways, which remains a challenge for the regeneration of studies,[5, 6] thus limiting rehydrogenation efforts. B-N hydrogen storage materials. Although significant advances were recently reported for The low-valent chromium fragment {Cr(CO)3} was tar- the regeneration of spent AB fuels by alternative path- geted as a platform capable of binding borazine and ways,[4c,d] these procedures utilize highly toxic and high- subsequently mediating the stepwise reduction of the ring. energy reductants (hydrazine and alkyl tin hydrides), which Prior studies on analogous arene–{Cr(CO)3} adducts showed negatively impact the net energy balance for the hydrogen that the sequential addition of hydride and proton equivalents storage system.