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Thiocarbonyl Complexes of Chromium and Tungsten Bernard Duane Dombek Iowa State University

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Thiocarbonyl Complexes of Chromium and Tungsten Bernard Duane Dombek Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1975 Thiocarbonyl complexes of chromium and tungsten Bernard Duane Dombek Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Dombek, Bernard Duane, "Thiocarbonyl complexes of chromium and tungsten " (1975). Retrospective Theses and Dissertations. 5413. https://lib.dr.iastate.edu/rtd/5413 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technoiogicai means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1.The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image. You will find a good image of ihe page in the adjacent frame. 3. When a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It is customary to begin photoing at the upper icit® ^ f A iiaiiu uuiiicBA A Aw ui— ^ aA laiyc9 ^ ^ A miccia A aiiu^ ^lu uuiiuiiucA A m # a uiiuiuitig'a ^ ^ a • ... iiuaii^ iciLV A >.lu 4» right in equal sections with a small overlap. Sf necessary, sectioning is continued again — beginning below the first row and continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essentia! to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. 5. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. Xerox University Microfiims 300 North Zeeb Road Ann Arbor, Michigan 48106 75-25,325 DCMBEK, Bernard Duane, 1949- mrOCARBONYL COMPLEXES OF CHRCMIUM AND TUNGSTEN. Iowa State University, Ph.D., 1975 Chemistry, inorganic Xerox University l\/licr0films, Ann Arbor, Michigan 48106 THIS DISSERTATION HAS BEEN MICROFiLMED EXACTLY AS KcCtiV Thiocarbonyl complexes of chromium and tungsten by Bernard Duane Dombek A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Chemistry Major: Inorganic Chemistry Approved: Signature was redacted for privacy. Signature was redacted for privacy. Signature was redacted for privacy. For the Graduate College Iowa State University Ames, Iowa 1975 I I TABLE OF CONTENTS Page LIST OF SYMBOLS AND ABBREVIATIONS ' I. INTRODUCTION 1 II. REVIEW OF THE LITERATURE 2 A. Carbon Monosulfide 2 B. Metal Thiocarbonyl Complexes 7 III. EXPERIMENTAL 18 A. General 'lo B. Spectra 18 C. Kinetic Experiments 19 D. Preparation and Reactions of Complexes 20 IV. RESULTS AND DISCUSSION 53 A. Attempts to Prepare Thiocarbonyl Complexes 53 B' T'ne Group vi n(CO)_(CS) ComDÎexes 59 C. Reactions at the Metal Center 68 D. Reactions at the Thiocarbonyl Sulfur Atom 106 E. Reactions at the Thiocarbonyl Carbon Atom 120 V. CONCLUSIONS 139 VI. SUGGESTIONS FOR FURTHER RESEARCH 142 VI I. LITERATURE CITED 144 Viii. ACKNOWLEDGMENTS 156 LIST OF SYMBOLS AND ABBREVIATIONS B a base bipy 2,2'-blpyridi ne Bu butyl CP cyclopentadi enyl cy cyclohexyl DAB CO 1,4-diazabicyclo [2.2.2] octane decali n decahydronaphthal ene diars o-phenylenebi s(dimethylars i ne) dîphos ethylenebis(diphenylphosphine) Et ethyl HA a protonic acid L a donor ligand Me methyl Oh pheny1 Py pyri di ne R an organic substituent group S a coordinating solvent molecule THF tetrahydrofuran TMS tetramethylsilane tr!phos bi s(2-dîphenyî phosph inoethyi) phenylphosphi ne X a halogen ] I. INTRODUCTION The thiocarbonyl ligand has recently attracted research of both theoretical and experimental nature because of its similarity to the familiar carbonyl ligand. The CS ligand is one of the simplest pos­ sible variations of the CO ligand, and can thus be considered as a "perturbation" of the carbonyl. The study of its complexes may there­ fore enhance the understanding of bonding and reactions of transition metal carbonyls in general. The main barrier to the extensive study of transition metal thiocarbonyl complexes is the difficulty of initial formation of the metal-CS bond. Carbon monosulfide, unlike carbon monoxide, is unstable under normal levels of temperature and pressure. Therefore, few metal thiocarbonyl complexes were known when this work began, and surprisingly little was known about the chemical properties and reactions of the complexes or the coordinated ligand. The available evidence, however, indicated that the CS ligand was a stronger pi-acceptor than CO and thus was iTiore strongly bound to the metal atom. The thiocarbonyl ligand also appeared to be more reactive than its oxygen analog. The field of transition metal thiocarbonyl chemistry was thus regarded as a potentially fruitful area of research. It was with the hope of preparing thiocarbonyl complexes suitable for spectroscopic and chemical study that this work was undertaken. 2 M. REVIEW OF THE LITERATURE A. Carbon Monosulfide 1. Preparation and properties of carbon monosulfide For many years carbon monoxide was the only formally divalent carbon compound known. Since it was expected that a sulfur analog should also be preparable, chemists made many attempts to form carbon monosul­ fide, which was anticipated to be a gas at room temperature. Several reactions were reported to give a polymeric form of CS; in one, CS^ was exposed to sunlight for several months,^ and a similar polymeric product was obtained from the reaction between Ni(CO)^ and ClgCS- Dewar and Jones,^ in 1910, were the first to observe monomeric CS, prepared from gaseous CSg by a high-frequency discharge. They were able to condense a liquid at the temperature of liquid air which exploded on warming to 4 give a brown polymeric solid. Shortly thereafter, J. J. Thompson reported that the mass spectrum of CS^ showed a strong peak at rr/s vvher. an electric discharge was passed through the CS^ vapor. Soon the elec- 5-11 tronic spectrum of carbon monosulfide was investigated. This pro­ vided a certain method for detection of the CS molecule. Carbon monosulfide has been shown to be a product in the following reactions: ] 2" ]8 a. Photolysis of CS^ in the vapor phase b. Photolysis of CS2 in a matrix^^'^' c. Thermal CS^ dissociation^^ 3 3 12 27-34 d. Dissociation of CS^ in a high-frequency discharge ' ' e. Reaction of CS^ with 0 atoms^'^^ f. Reaction of CS^ with S atoms 39 g. Dissociation of COS in a high-frequency discharge 40 h. Reaction of MnS and C at elevated temperature i. Ar and Xe metastable atom energy transfer to CSg, COS, and ClgCS^^ 42 Carbon monosulfide has also been observed in the upper atmosphere and 43 in interstellar space. The best synthetic method for preparing use- 32 34 fui quantities of CS is by the use of a high-frequency discharge. ' The stability of CS in the gas phase is determined by many factors, including the temperature, partial pressure, dimensions of the container, 8 16 29 44 and the condition of the surface of the container. ' ' ' In a clean vessel the lifetime of CS at 40-80 torr is on the order of minutes, but it is reduced to seconds once a surface deposit is formed. The loss of CS from the gas phase is a wall reaction, and the data are not consistent with the simple polymerization of the molecule. A carbon-rich solid and CSg are reported to be the products of the surface decomposition. The decomposition of CS in the condensed phase is also apparently 32 not a simple polymerization. Steudel has concluded that the condensed (-190°) product resulting from passing CSg through a discharge is a mixture of CSg, CS, and C^Sg- As the mixture is slowly warmed, the amount of CS decreases as more C^Sg is produced, perhaps by disproportion- ation of the CS. The polymer that results often contains free sulfur 4 which is extracted with CS2. The composition of the product thus obtained corresponds to a pwlymerized mixture of CS and C^Sg in a ratio of about 3:1. Different methods of preparation give polymers of different prop- 2 12 29 erties, ' ' and it appears that there is no simple "CS polymer". These polymerization reactions point out the high reactivity of CS even at low temperatures. Steudel concluded that this property makes 32 its isolation in a pure state impossible. Recent spectroscopic studies of CS include the vacuum ultraviolet 45 absorption spectrum. an emission study in the vacuum and near ultra­ violet regions,^^ and spectroscopic studies of excited electronic states.Several microwave studies have been performed. By this method, the internuclear distance^^ has been determined to be 1.5349^0.0002% and the dipole moment^^"^^ reported to be 1.958± 0.005D, in the direction -CS+.
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