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And Tungsten(IV) and the Oxochlorides of Tungsten(VI)

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And Tungsten(IV) and the Oxochlorides of Tungsten(VI) University of the Pacific Scholarly Commons University of the Pacific Theses and Dissertations Graduate School 1965 The Binary Halides Of Molybdenum(IV) And Tungsten(IV) And The Oxochlorides Of Tungsten(VI) Edward Roy Epperson University of the Pacific Follow this and additional works at: https://scholarlycommons.pacific.edu/uop_etds Part of the Chemistry Commons Recommended Citation Epperson, Edward Roy. (1965). The Binary Halides Of Molybdenum(IV) And Tungsten(IV) And The Oxochlorides Of Tungsten(VI). University of the Pacific, Dissertation. https://scholarlycommons.pacific.edu/uop_etds/2865 This Dissertation is brought to you for free and open access by the Graduate School at Scholarly Commons. It has been accepted for inclusion in University of the Pacific Theses and Dissertations by an authorized administrator of Scholarly Commons. For more information, please contact [email protected]. ... ·~ ' .. .: ~ .. \, THE BINARY HALIDES OF Iv10LYBDENUM(IV) AND TUNGSTEN(IV) AND THE OXOCHLORIDES .OF 'rUNGSTEN (VI) A Dj. ssertation Presented to the Faculty of the Department of Chemistry University of the Pacific In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy by Edward Roy Epperson June 1965 This diss~rtaHon, written al}d submitted qy EdwardHoy Epperson is appJ"oved for r~commef\dation to the Gra~uate Council,· Vniver ~ity Qi the PCl-cific. · +-~~~~~~~~~~~~~------ ---- Department Chi;~.irrpan er .Qean:. Dissertation C~n:nmitt~e: v{~, ~~Vhairman /ZJ . , . A @. e::l:'J'~""* P . ·.· ~~-~::: .. _;~iil.ill. ACKNOWLEDGEMENTS The author wishes to express his sincere appreciation well-rounded program of graduate studies, to the entire Faculty of the Department of Chemistry for their invaluable implementation of these graduate studies, and especially to Dr. Herschel G. Frye for his continuing interest in and direction of the research project that has found expression in this dissertation. Appreciation is also extended to Dr. J. E. Danieley, President of Elon College, the National Science Foundation, the Piedmont University Center of North Carolina, and the North Carolina Academy of Sciences for the provision of funds in support of this program of studies and research activities. I I TABLE OF CONTENTS CHAPTER PAGE I. INTRODUCTION . 1 II. TETRAFLUORIDES . 3 Molybdenum Tetrafluoride . • 3 Preparation . • 3 Physical properties • . • . 4 Chemical properties • . • • . • • . 4 Tungsten Tetrafluoride • • • • 0 • • 6 Preparation . • . 6 Physical properties . 6 Chemical reactions . $ III. EXPERIMENTAL METHOD OF KNOX AND TYREE • • • • • • 9 Apparatus . • • • . 9 Reaction vessel . 9 Inert atmosphere enclosure . 10 · Procedure . 12 IV. TETRACHLORIDES . • • • • 0 • . 20 Molybdenum Tetrachloride . • • • 20 Preparation . • . 20 Early syntheses . • • . 20 Thermal decomposition of molybdenum trichloride • . • . • • . 20 -= Reduction of molybdenum pentachloride • • • 21 v CHAPTER PAGE Reflux of molybdenum dioxide with chlorocarbons . 23 ~- The method of Knox and Tyree . 23 Method of analysis of MoC14 • . • • • • • • . 30 Physical characteristics . 31 ~------------------~S~t~a~b~i~l~i~ty • • • • • . 31 Chemical reactions • • • • • • • • • e • • • 32 With water and acids . 32 With nitrogen donors . 32 V'vith phosphorus and arsenic donors 34 With oxygen donors . 34 Tungsten Tetrachloride . 36 Preparation . 36 Reduction of tungsten hexachloride, WC16 36 The method of Knox and Tyree . 37 Method of analysis of wc1 4 • • • • • • • 41 Physical characteristics . 42 Stability ..... 45 ~ E Chemical reactions . 45 I With water . 45 With nitrogen donors . 45 With other donors . 46 v. TETRABROMIDES • • • . • . 47 Molybdenum Tetrabromide • • • • • 0 • 47 vi CHAPTER PAGE Preparation . • . 47 Reactio~ of MoBr3 with Br2 • • • • • • • • 47 The method of Knox and Tyree • • • • • • • 48 Other syntheses . · • • . 48 Physical characteristics . 48 J----------------""S'-"-'tab_il_it_y____._·._._._._._._._._.~.-·-·-·-·-·-·-· __4_3~__ ___ Chemical· reactions . 50 With water . 50 With diarsine . 50 Tungsten Tetrabromide • . 50. Preparation . • • 50 Reduction of tungsten pentabromide • • • • 50 The method of Knox and Tyree . 51 Method of analysis of WBr4 . 52 Physical characteristics • • • • • • • e • • 52 Stability ••..• • • . 54 Chemical reactions . 54 With water . 54 i i With nitrogen donors . 54 I VI. TETRA IODIDES . 55 Molybdenum Tetraiodide . 55 Preparation . • . 55 Physical properties . 56 Chemical characteristics . 56 vii CHAPTER PAGE Tungsten Tetraiodide " . 56 Preparation . 56 Physical properties . 5S Chemical characteristics • . 5S VII. OXOCHLORIDES OF TUNGSTEN(VI) . 60 Tungsten Dioxodichloride . 60. Preparation . 60 Chlorination of wo3 . • . • • 60 Chlorination of wo2 . • .. • • 61 Physical properti.es . 61 Chemical properties . • . • • . • 61 Tungsten Oxotetrachloride . • • • • 63 Preparation . 63 Chlorination of wo3 • • • • • • • • • • • 63 Chlol:'ination of a W-vm 2 Mixture • • • • • 63 The method of Knox and Tyree • . ... 64 Method of analysis of WOC1 . • • . • . 65 4 Physical properties . 65 i Chemical properties . 6S I VIII. SUMMARY . 69 BIBLIOGRAPHY • e e e e * e • e e e • e • • e e e e e G 72 APPENDIX . Sl LIST OF TABLES ~ = ff TABLE PAGE ·~ I. Physical and Physicochemical Properties ~- of Molybdenum Tetrafluoride . • . • . • • . 5 II. Physical and Physicochemical Properties of Tungsten Tetrafluoride . • • . • 7 III. Analyses of Mo0 2-cc14 Reaction Product • • • • • 27 IV. Physic~l and Physicochemical Properties of Molybdenum Tetrachloride . • . 35 v. Analyses of wo 2-cc14 Reaction Product • • • . • 39 VI. Physical and Physicochemical Properties of Tungsten Tetrachloride . • • . 43 ~ E ~ VII. Physical and Physicochemical Properties E ~ of Molybdenum Tetrabromide . .. • . • • • • • 49 VIII. Physical and Physicochemical Proper~ies of Tungsten Tetrabromide . • . • • • • 53 IX. Physical and Physicochemical Properties of Molybdenum Tetraiodide . • . • • . 57 ~ x. Physical and Physicochemical Properties E of Tungsten Tetraiodide I= . • . • • • • • • • 59 - --- XI. Physical and Physicochemical Properties - of Tungsten Dioxodichloride • . • • • • • 62 ~-- ~ XII. Physical and Physicochemical Properties ~ - - of Tungsten Oxotetrachloride . • . • • • • • 66 - LIST OF FIGURES FIGURE PAGE l. Glass Reaction Vessel . • • • • • 14 2. Container for Removal of Opened Reaction Vessel to Dry-Box • . 18 -= CHAPTER I INTRODUCTION The binary tetrahalides of molybdenum and tungsten have been prepared and characterized to some degree. The tetrachlorides and tetrabromides have been studied exten- The tetrafluorides and the tetraiodides have not been studied so thoroughly and little is knoWn about them. A general preparative method for anhydrous metal chlorides is that of Knox and Tyree in which a metal oxide and carbon tetrachloride are heated to varying temperatures in a sealed glass tube. The glass tube is contained in a metal bomb with carbon tetrachloride in it to equalize the pressure. In previous syntheses utilizing this method, Knox etcal. (1957) have reported ReC1 5, TcCl4, MoCl5, WC16, and TaCl5, while Epperson et al. (1963) have reported A1Cl3 , & Fec13 , NbC1 5 , and Zrc14 . In all of these syntheses, the = oxide of highest oxidation state produced the highest I chloride; e.g., wo = WC16, Moo = Moc1 . The question 3 3 5 then arose as to whether this preparative procedure might be applied to the synthesis of the tetravalent chlorides and bromides of molybdenum and tungsten. 2 It was the purpose of this current study to investigate the reaction of molybdenum and tungsten dioxides with carbon tetrachloride and bromoform (via the method of Knox and Tyree) to produce anhydrous molybdenum and tungsten tetrachlorides and bromides and to determine whether the method is a reliable one for the synthesis of these com- ~----------pounds. Out of this grew an investigation into the prep~a=r~a~-~·------­ tion of the oxochlorides of tungsten(VI) using the same preparative technique. The results of this study are here set forth. An attempt is made to systematize the published material on the synthesis and properties of the binary halides of molybdenum(IV) and tungsten(IV) and the oxochlorides of tungsten(VI). Extensive calculations have been carried out by A. Glassner in 1957 and L. Brewer and co-workers in 1950 on the estimation of thermochemical and thermodynamic data for the tetrahalides of molybdenum and tungsten. These data are in general based on analogy with compounds of neighboring elements in the Periodic Table. Even though these values are subject to uncertainty, they are included here for comparative purposes. =~ ------- -------·· ---- ---- CHAPTER II TETRAFLUORIDES I. MOLYBDENUM TETRAFLUORIDE J. J. Berzelius (in 1826) first reported the preparation of a molybdenum-fluorine 'COmpound purported to h:ave------th-e~st_o-icniometry of-Mo:B'~Tnis was achieved by the action of hydrofluoric acid on hydrated molybdenum dioxide. A red solution resulted which on slow evaporation yielded a black, thermally unstable, crystalline residue. This work has not been successfully duplicated and there was doubt as to the existence of molybdenum tetrafluoride until the researches of R. D. Peacock in 1957. Preparation The only reported preparation of pure molybdenum tetrafluoride is that of Peacock. By the action of gaseous fluorine on molybdenum hexacarbonyl at -75° C., an olive~ green solid and carbon monoxide are formed. The olive-green solid has an apparent formula of Mo 2F9 and on being heated to 170° c. ill vacuo yields MoF 5 as a distillate and MoF4 as the residue.
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