Durham E-Theses Electrosynthetic and other studies of sulfur imides and aromatic thiazenes Clarke, H. G. How to cite: Clarke, H. G. (1974) Electrosynthetic and other studies of sulfur imides and aromatic thiazenes, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/8276/ 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 ELECTROSYNTHETIC AND OTHER STUDIES OF SULFUR IMIDES AND AROMATIC THIAZENES by H.e;. CLARKE, B.Sc. A thesis submitted for the degree of Doctor of Philosophy in the University of Durham September 1974 6 DEC 1974 HE0T10* LIBRA Acknowledgments The author wishes to express his gratitude to Sr. A.J. Banister, under whose supervision this research v/as carried out, for his unflagging enthusiasm, constant interest and valuable advice throughout the whole period of study. My thanks are also due to the Science Research Council and Staveley Chemicals Limited for providing a research grant, to the Senate of the University of Durham for research facilities, to many of the departments technical staff and to Dr. O.R. Brown of Newcastle University, for assistance in the research, and to Staveley Chemicals Limited for valuable industrial experience. Finally, my thanks are due to Mrs. Janet Dunford, for the many hours spent in typing this thesis. Memorandum The work described in this thesis was carried out in the University of Durham "between September 1970 and September 1973* apart from:- (i; a period in December 1970 at Newcastle University, studying the electrolytic reduction of tetrasulfur tetranitride in organic solvents, and (ii) three months between July and September 1972 at Staveley Chemicals Limited (See Chapter 8). The work described in this thesis has not been submitted for any other degree and is the original work of the author, except where acknowledged by reference. Parts of this thesis have been the subjects of the following publications:- 1. Banister, A.J., and Clarke, H.G. "The Preparation of Cyclopentathiazenium (S^N^+) Salts and some Observations on the Structure of the Cyclopentathiazenium Cation". J. Chem. Soc. Dalton, 1972, 2£, 266l. CA. 1973, 18, 23432s. 2. Zahradnik, R., Banister, A.J., and Clarke, H.G. "Electronic Spectrum of the Pentathiazyl Cation". Collect. Czech. Chem. Communs., 1973, j5§, 998. CA. 1973, J_9_, 36830r. 3. Banister, A.J., and Clarke, H.G. "Preparation of Cyclopentathiazenium (S,-N,-+) Salts". Inorganic Synthesis (in press). 4. Banister, A.J., Clarke, H.G., Raimant, I., and Shearer, H.M.M. "The Structure of Thiodithiazyl Chlorodisulfate, (S^Ng SgOgCl), and its Preparation from Thiodithiazyl Monochloride, S^N^Cl". J. Inorg. Nuclear Chem. (in press) -(iii)- To my Mother and Father "Great are the works of the Lord, studied "by all who have pleasure in them". Psalm 111, v. 2 -(iv)- Abstract This thesis describes the work carried out by the author between September 1970 and September 1973. The electrolysis products of sulfur and 3^N^ in liquid ammonia, and S^N^ in organic solvents were studied with a view to devising improved routes to S^NH, S^(NH)^ and other imides. The reactions of these tv/o compounds as model sulfur imides were also investigated. Addition reactions of (NSCl)^ were studied because it is the cheapest source of SN and NSC1 fragments, and because it was hoped to convert the imides into SN compounds with exocyclic S-Cl bonds. It was found that (NSCl)^/metal chloride adducts behaved as a source of NS+ ions in thionyl chloride solution, + + which reacted with SC1_ and S.N. to form the cations SnNCl_ and S,-Nc 2 4 4 2 2 5 5 respectively. The structures of these two cations were discussed, in particular + the structure and reactions of SCNC as a member of the "electron rich" aromatic 5 5 series of sulfur-nitrogen compounds. Other as yet unknown species were predicted as also being members of this series, and their possible stability and preparative routes discussed. A study was also carried out on the little investigated compound 2+ "S^NgCl". The chlorodisulfate derivative:- S^N^ (ClS20g~)2 - was prepared, and the structure (obtained from x-ray crystallographic studied) discussed with reference to the unusual bonding observed in this compound. Finally, a summary of the work carried out at Staveley Chemicals Limited is included. -(v)- CONTEHTS Page CHAPTER 1. Introductory Review. Introduction 1 (A) Tetrasulfur Tetranitride 2 1. Physical Properties 2 2. Preparative Routes 4 (i) Preparation from sulfur dichloride and ammonia 4 (ii) Preparation from SgClg and ammonium chloride 5 (iii) Preparation from azides and SgCl^ or S^N^Cl 6 (iv) Preparation from ammonia and sulfur fluorides 6 (v) Preparation of S^N^ from its elements 7 (vi) Preparation of S^N^ using liquid ammonia 7 (vii) Other reactions producing S^N^ 8 3. The Structure of Tetrasulfur Tetranitride 8 (i) Introduction 8 (ii) Bonding in S^N^ 9 (iii) S.N. structure, conclusion 16 4 4 4. S^N^ Inorganic Reactions 18 (i) Reactions involving ring contraction or expansion 18 (a) Chlorination 18 (b) Piuorination 18 (c) Reaction with bromine 19 (d) Ring contraction to S^N^+ salts 19 (e) Ring expansion to S^N,-+ salts 20 (f) Ring contraction to other sulfur nitrides 20 (ii) Reduction of S.N. 20 * ' 4 4 (iii) Oxidation of S.N 20 -(vi)- Page (iv) Reaction of S.N. with metals and metal compounds 22 (a) Adduct formation by S^ 22 (b) Reactions of S.N. with other metal compounds 25 (i) Reactions of S^N^ with metal halides 27 (II) Reaction of S^N^ v/ith metal carbonyls 28 (III) Reaction of S.N. with metals 28 (IV) Reactions of S .N with metal compounds in liquid ammonia 29 (v) Reactions of S.N with metal halides in thionyl chloride 44 29 (vi) Reaction of S^N^ with phosphorus compounds 29 (a) PC15 29 (b) Triphenyl phosphine Ph^P and (CgH-^^P 30 (c) Phenyl dichloro-phosphine PhPCl^ 30 (vii) Reaction of S^ v/ith CN" 31 (viii) Ion and free radical formation by S^N^ 31 (ix) Reaction of S^N^ with free radicals 33 (x) ^^4» hydrolysis and decomposition reactions 33 5. Organic Chemistry of S^N^ 34 (i) Reactions of S^N^ as an inorganic diene 34 (ii) Reactions of S.N. with negatively-substituted acetylenes 3° (iii) Reactions of S.N. with saturated and aromatic hydrocarbons 37 (ivj Reaction of S^N^ with Grignard Reagents 39 (v) Reaction of S^N^ v/ith acetyl chloride 39 (vi) Reaction of S^N^ with substituted diazo methanes 39 (vii) Reaction of S.N. with amines 40 -(vii)- Page (B) Other Sulfur Nitrides 42 1. Introduction 42 2. Disulfur Dinitride 42 (i) Preparation 42 (ii) Physical properties 42 (iiij SgNg Molecular structure 43 {iv) S^Ng Reactions 43 (a) Polymerisation 43 (b) Adduct formation 44 (c) Ring expansion 44 (d) Formation of thionitrosyl complexes 44 (e) Decomposition and hydrolysis 44 3. Tetrasulfur Dinitride S.N„ 45 4. Polythiazyl (SN)^ 46 (CJ Sulfur-Nitrogen Chlorine Compounds 48 1. Thiotrithiazyl Chloride S^Cl 48 (ij Preparative routes 48 (a) Preparation from S^, S^Clg or (NSCl)^ 48 (b) Reaction of sulfur halides with ammonia 48 (c) Reaction of sulfur chlorides with azides 48 (d) Preparation from S^NgCl 49 (e) Preparation from S^N^ and bromine 49 (ii") Physical properties 49 Uii) Structure 49 (iv) S,N,C1 Reactions 50 4 3 (a) Salt formation 51 (bj Ring expansion 52 -(viii)- Page (c) Hydrolysis and decomposition 52 (d) Reactions with triphenyl phosphine 52 (e) Reactions with amines 52 (v) S^Cl uses 52 2. Thiodithiazyl Bichloride SJ^Cl^ 53 (i) S5N2C12 Structure 53 (ii) SjNgClg Preparative routes 54 (a) Preparation from sulfur, ammonium chloride and S2C12 54 (bj Preparation from trithiazyl trichloride and S2C12 54 (cj Formation from S^N^ in thionyl chloride 54 (d) Chlorination of S^Cl 54 (iii) S NgClg Reactions 54 (iv) SjN2 Clg Physical properties 55 3. Thiodithiazyl Monochloride SJT^Cl 55 4. Trithiazyl Trichloride (NSClj, 56 (i) Physical properties 56 ^ii) Preparative routes 57 (a) Chlorination of S^ or S^Clg 57 (b) Reaction of ammonium chloride with SgCl,, 57 (c) Reaction of S2C12 with activated nitrogen 58 (iii) Structure of (NSCi;^ 58 UvJ (NSCl), Reactions 59 3 (a) Fluorination 59 (bj Adduct formation 59 (c) Hydrolysis and decomposition 60 ^d; Reaction with imides 60 (e) Reaction with epoxides 60 -(ix)- Page 5. Trithiazyl Monochloride S,N.,C1 6l 6. The Compounds; (S^Cl)^ S-^NQCI^ and S^N^Cl^ 61 (D) The Sulfur Imides 62 1. Introduction 62 2. The Sulfur Imides based on the SQ ring. Structure and Bonding 62 3. Structures of the other Sulfur Imides 64 4. Imides with N-N bonds 64 5. Imides based on other rings 65 6. Sulfur Imides. Physical Properties 65 7. Sulfur Imides. Preparative Routes 66 (i) Preparation from ammonia and chlorosulfanes 66 (ii) Preparation of S^NH using hydrazine 67 (iii) Preparation of S^NH using azides 67 (iv) Reduction with LiAlH^ or Raney nickel 67 (v) Preparation using liquid ammonia 67 (vi) Preparation of other imides 67 (a) S4(NH)4 67 (b) SUN2 68 (c) Preparation of the coupled ring nitrides S„N-S -NS„ 68 7x7 (d) Preparation of imides containing N-N bonds 68 (e) Imide derivatives 68 8.