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Durham E-Theses Durham E-Theses Alkoxyberyllium alkyls and related compounds Fishwick, A. H. How to cite: Fishwick, A. H. (1967) Alkoxyberyllium alkyls and related compounds, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/8530/ 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 ALKOXYBERYLLIUM ALKYLS AND RELATED COMPOUNDS. - by - A.H. FISHiVICK, 3.Sc. A thesis submitted for the degree of Doctor of Philosophy. University of Durham. July, 1967. "K , Stall*.. J (ii) ACKNOWLEDGMENTS« The author wishes to express his sincere gratitude to his supervisor, Professor G.E. Coates, for his constant help and encouragement throughout the time in which this work was carried out. Thanks are also due to Dr. N.A. Bell and Dr. K. Wade for many helpful discussions, and to Mr. P.D. Roberts for the loan of a typewriter. The author is also indebted to Ethyl Corporation for a Research Studentship. (iii) MEMORANDUM. The work described in this thesis was carried out in the Department of Chemistry of the University of Durham between October, 1964 and June, 1967. It is, except where acknowledged by reference,, the original work of the author, and it has not been submitted for any other degree. Part of this work is the subject of a paper submitted to the Journal of the Chemical Society, [J. Chem. Soc(A), 6/1473, in press]. (iv) SUMMARY. Some reactions of dialkylberyIlium compounds with 'weak acids*, yielding 'internal' coordination complexes, have been examined. With secondary amines, in equimolar amounts, a series of aminoberyIlium alkyls, (RBeNR^)^, is formed. Their degree of association, n, depends upon the size of the groups R and R'. When R' is methyl, trimers, are exemplified by (EtBeNMe^)^» formed, and (MeBeNEt^)3 is also trimeric, but for larger R and R', dimers, such as (Me3eNPh2)2 and (EtBeNPh2)2, occur. These compounds must all be formulated with three-coordinate metal, and some of their reactions with pyridine and 2,2'-bipyridyl were investigated. Crystalline complexes, [R(NR')Be.py]0, R(NR2)Be.py2 and R(NR2) B e . b i py , can be formed, but the reactions are sometimes complicated by disproportionation processes. The adduct, Bu^Be.NHMe,,, is described. Alcohols, with dimethylberyIlium, yield tetramers, (MeBeOR)A> but lower degrees of association result from the use of bulkier organic groups, as illustrated by t t (EtBeOCEt3)3, (MeBeOCPh3)2 and (Bu BeOBu )2« When prepared in diethyl ether, some of the products, e.g., MeBeOPh.OEt , retain ether as coordination complexes. The pyridine adducts, Me(OMe)Be.py2» and Me(OBu )Be.py are discussed. Reaction with two molar proportions of alcohol t gives the alkoxides [Be(OMe)2]x, [Be(OBu )2]3 and [Be(OCEt3)2]2. The proton magnetic resonance spectra of some of these compounds show some unexpected splittings of signals and, in the cases of (MeBeOBut) and [Be(OBu )2]3» pronounced solvent effects. Thiols yield tetramers, (RBeSR') , presumably (v) containing four-coordinate beryllium, but, in contrast to the alkoxy- derivatives, no compounds containing three- coordinate metal were isolated. Many of the reactions 3e and resulted in disproportionation to R2 (R'Sj^Be, but a series of adducts of some of these products, (RBeSR')^, which are unstable to disproportionation, and of the t tetramer, (EtBeSBu )4, with the bases ether, tetrahydrofuran, pyridine and 2, 2'-bipyridy1, was t obtained. The alkyl sulphides, [Be(EtS) ] and [Be(Bu S)0] are described. Diethylberyllium and selenophenol give (EtBeSePh.OEt2)2 or (PhSe)2Be.0.65 OEt^, depending on the reactant ratios. MethylberyIlium- 2-dimethylaminoethoxide oligomer, 2-dimethylaminoethylsulphide trimer, ethylberyllium 2-methoxyethoxide tetramer, and the pyridine adducts, Pr„Be.py and Bu^Be.py0 were prepared. CONTENTS» Page. AC KNOW LSD Gill EN T 3 . ii ^^^NDJJM^ iii SUMMARY^, iv INTRODUCTION. 1 Electron donor-acceptor complexes of organoberyIlium compounds. 2 DimethylberyIlium. 3 DiethylberyIlium. 6 Di-isopropylberyIlium. 8 Di-t-butylberyllium. 8 DiphenylberyIlium. 10 Bipyridyl complexes. 11 'Internal' coordination complexes. 13 Group II elements. 14 Beryllium. 14 Magnesium. 24 Zinc. 28 Infrared and proton magnetic resonance spectra. 37 Cadmium. 38 Other Group II elements. 40 Group III elements. 41 EXPERIMENTAL. 48 Apparatus and techniques. 48 Analyses. 51 Preparation and purification of starting materials and solvents. 55 EXPERIMENTAL RESULTS. 62 Memoranda. 62 Page. Reactions with amines. 63 Reaction of dimethylberyIlium with: Dimethylamine. 63 Diethylamine. 63 Di-n-propylamine. 64 Diphenylamine. 65 Reaction of diethylberyIlium with: Dimethylamine. 66 Diethylamine. 67 Diphenylamine. 68 Reaction of di-isopropylberyllium with: Dimethylamine. 68 Pyridine. 69 Reaction of di-t-butylberyllium with: Dimethylamine. 70 t-3utylamine. 7 3 Pyridine. 74 Reaction of dimethylaminolithium with: Beryllium bromide. 75 Beryllium chloride. 75 Reactions of aminoberyIlium alkyls with bases. 76 Dimethylamino(methyl)beryllium. 76 Diphenylamino(methyl )beryllium. 78 Diphenylamino(ethyl)beryIlium. 80 Di-n-propylamino(methyl)beryIlium. 83 Bis(dimethylamino)beryIlium. 83 Reactions vvith alcohols and phenol. 85 Reaction of dimethylberyllium with: Methanol. 85 Ethanol. 86 n-Propanol. 86 Page. iso-Propanol. 87 t-3utanol. 88 Diphenylmethanol. 90 Triphenylmethanol. 91 2-Dimethylaminoethanol. 93 Phenol. 93 Reaction of diethylberylliura with: Triethylrnethanol. 95 2-Methoxyethanol. 96 Phenol. 97 Reaction of di-isopropylberyllium wi th : Methanol. 98 Reaction of di-t-butylberyIlium with: Methanol. 99 t-Butanol. 100 Reaction of dimethylberyllium with: Ethylene oxide. 101 Di-t-butyl peroxide. 101 Reactions with aldehydes and_ k^tojes._ 102 Reaction of dimethylberyllium with: Acetaldehyde. 102 Acetone. 102 Reaction of diethylberyIlium with: Diethyl ketone. 103 Reactions of alkylbery11ium a1kpxides with bases. 103 Methylberyllium methoxide. 103 Methylberyllium t-butoxide. 105 Methylberyllium phenoxide diethyl ether complex. 106 t-Butylberyllium t-butoxide. 106 Beryllium t-butoxide. 107 Page. Reactions with thiols and thiophenol. 108 Reaction of dimethylberyIlium with: iso-Propylthiol. 108 t-Butylthiol. 109 Thiophenol. 110 2-Dimethylaminoethanethiol. 110. Reaction of diethylberyllium with: Methanethiol. Ill Ethanethiol. 112 iso-Propylthiol. 113 t-Butylthiol. 114 Reaction of di-isopropylberyIlium with: Ethanethiol. 115 iso-Propylthiol. 115 t-Butylthiol. 116 Reaction of diethylberyllium with: Diethyl disulphide. 116 Reactions of alkylberyIlium alkylsulphides with bases. 117 Impure ethylberyIlium methylsulphide. 117 Ethylberyllium ethylsulphide. 117 EthylberyIlium isopropylsulphide. 118 Ethylberyllium t-butylsulphide. 118 iso-Propylberyllium ethylsulphide diethyl ether complex. 120 Impure isopropylberyllium isopropylsulphide. 121 Beryllium t-butylsulphide. 122 Reactions with selenophenol. 12 4 Reaction of diethylberyllium with: Selenophenol. 124 Page. DISCUSSION. 126 Reactions with amines. 126 Proton magnetic resonance spectra. 134 Di-t-butylberyllium-dimethylamine adduct. 134 Reaction of di-t-butylberyIlium with t-butylamine. 136 Reactions of di-isopropy1-, and di-t-butyl- beryllium with pyridine. 136 Reactions with alcohols and phenol. 137 Reactions of alkylberyIlium alkoxides with bases. 139 Infrared and proton magnetic resonance spectra. 143 Other reactions producing alkoxy compounds. 151 Reactions with thiols and thiophenol. 154 Reactions of alkylberyIlium alkylsulphides with bases. 158 Infrared and proton magnetic resonance spectra. 162 Reactions with selenophenol. 164 Reactions with molecules which contain a chelate group. 166 REFERENCES. 168 INTRODUCTION. INTRODUCTION. The work described in this thesis is concerned with the preparation of amino-, alkoxy-, and thio- derivatives of alkylberyIlium, their coordination chemistry, and their molecular complexity in solution. In this introduction, the following topics, each of which has a particular relevance to the work investigated, are discussed: a) the electron donor-acceptor complexes of organoberyIlium compounds. b) the 'internal' coordination complexes of beryllium and other Group II elements, and, more briefly, c) the 'internal' coordination complexes of the elements of Group III. 2 2 Beryllium has the electronic configuration Is 2s and due to the small size and consequent high polarising power 2+ of the dipositive cation, Be , forms covalent compounds almost exclusively. Even beryllium fluotide, which might be expected to be the most ionic compound of beryllium, conducts electricity only poorly in the fused state. The fact that the ionisation potentials of beryllium are high, the first being 215 and the second 420 k.cal.mole"'1, is in keeping with these observations, and suggests that free, dipositive beryllium ions do not exist in its compounds. Beryllium compounds have covalencies of two, three or four for the metal atom. Coordination
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