30 September 1966 RSIC-591 FERROGENE and FERROGENE
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f 30 September 1966 RSIC-591 FERROGENE AND FERROGENE DERIVATIVES by William P. McNutt Charles U. Pittman, Jr. DISTRIBUTION OF THIS DOCUMENT IS UNLIMITED Research Branch Redstone Scientific Information Center Research and Development Directorate U. S. Army Missile Command Redstone Arsenal, Alabama 35809 ABSTRACT This is an annotated bibliography covering ferrocene and its deriv- atives from 1962 to August 1966. Several review articles are listed which describe the unique characteristics of ferrocene since its dis- covery in 1951, its reactions, and some of its uses. Approximately 550 citations are listed. FOREWORD This bibliography of ferrocene and ferrocene derivatives was com- piled in response to a request from the Propulsion Laboratory, Research and Development Directorate, U. S. Army Missile Command. The survey was undertaken to provide a comprehensive listing of ferru_n_ chemistry literature throughout the world from 1962 to August 1966. The 1962 starting date was selected since the literature fromferrocene's discovery in 1951 has been well covered in a number of review articles, through 1961, many of which are included in Section VII. The principle sources searched were chemical abstracts, and documents of Redstone Scientific Information Center; however, many other journals and abstracting services, both foreign and domestic, were searched for contributing articles. Additional information con- cerning specific uses of ferrocene and ferrocene derivatives was obtained from Mr. Hans W. Sitarz, Manager, Army Programs, Thiokol Chemical Corporation, Huntsville Division, and from Rohm and Haas Company, Huntsville Division. Clarification of abbreviations and symbols used in this survey may be found in chemical abstracts. Dr. Charles U. Pittman, Jr. (First Lieutenant, U. S. Army) would like to thank the Propulsion Laboratory of the U. S. Army Missile Command for the time allotted for this work, and for other active support, in this regard, he would _._..y-_-_"I"_I""!iu_.._*_........_hank Messers N. C. White and C. W. Huskins. iii CONTENTS Page ABSTRACT . ................................... ii INTRODUCTION ................................ 1 LITERATURE CITED ............................. 5 BIBLIOGRAPHY ................................. 7 Section I. GENERAL STRUCTURE AND THEORY OF FERROCENE REACTIVITY AND BONDING ....... A. Ferrocenyl Carbonium Ions ................... 7 B. I_erricinium Ions and Salts ................... 16 C. Charge Transfer and w Complexes .............. 23 D. Protonated Ketones ......................... 26 E. Resonance and Inductive Effects ................ 27 F. Structure ............................... 38 G. Reactivity ............................... 53 Section II. SYNTHESIS OF FERROCENE AND FERROCENE DERIVATIVES .......................... 6O A. Ferrocene, Bridged Ferrocenes, and Multinuclear Ferrocenes .............................. 60 B. Alkyl, Dialkyl, and Polyalkyl Ferrocenes ......... 88 C. Acyl Ferrocenes .......................... 97 D. Aryl Ferrocenes .......................... 135 E. Olefinic and Alkynyl Ferrocene Derivatives ........ 139 F. Alcohols in Ferrocene Series ................... 155 G. Nitrogen Containing Ferrocene Derivatives ......... 163 H. Halogen Derivatives ........................ 182 I. Arsenic and Phosphorous Derivatives ............ 186 J. Organometallic Ferrocene Derivatives ........... 191 K. Sulfur Containing Derivatives .................. 196 L. Silicon Containing Derivatives ................. 205 M. Miscellaneous Derivatives .................... 216 Section III. REACTIONS OF FERROCENE DERIVATIVES ..... 231 A. Ferrocene, Bridged Ferrocenes,and Alkyl Ferrocenes. Z31 B. Olefinic I_errocene Derivatives and Alcohols in the Ferrocene Series ......................... Z47 V Page C. Acyl Ferrocene Derivatives ................... 251 D. Nitrogen Containing Ferrocene Derivatives ......... 269 E. Halogen Containing Ferrocene Derivatives ......... 283 F. Silicon, Sulfur, and Phosphorous Containing Ferrocene Derivatives ...................... 287 G. Organometallic Ferrocene Derivatives ............ 292 Section IV. FERROCENE POLYMERS .................. 304 A. Work in United States ....................... 304 B. Russian Effort ............................ 318 C. Other Nations ............................ 325 Section V, ANALYTICAL PROCEDURES ................ 335 A. Chromatography .......................... 335 B. X-ray Methods ........................... 338 C. Nuclear Magnetic and Electron Spin Resonance Spectroscopy ............................ 344 D. Infrared and Ultraviolet (Visible) Spectroscopy ...... 347 E. Mass Spectroscopy ......................... 353 F. Conductivity Measurements ................... 355 G. M6ssbauer Spectroscopy, Polarography, Microanalytical Techniques, and Other Analytical Procedures ....................... 357 Section VI. USES, PRODUCTS, AND COMMERCIAL APPLICATIONS ......................... 365 A. Propellant Additives ........................ 365 13. Electrical Properties, Insulators, Dielectrics, etc. 367 C. Products of High Temperature Stability, Radiation Stability, and Ultraviolet Absorbability ..... 372 D. Other Uses .............................. 382 Section VII. REVIEW ARTICLES ON FERROCENE ......... 387 AUTHOR INDEX ................................ 398 vi T INTRODUCTION In 1951 Kealy and Pauson at Sheffield University discovered dicyclopentadienyl iron, now commonly called ferrocene. This com- pound possessed properties _r1_ing_y _**_ ............... organometallic compounds, and this attracted the attention of chemists at large. Within a year Woodward, Rosenblurn, Whiting, and Wilkinson z'3 had recognized the unique sandwich structure of ferrocene. The strik- ing aromaticity of the cyclopentadienyl rings was demonstrated by Woodward, Rosenblum, and Whiting. The discovery of ferrocene stimulated intensive research in the cyclopentadiene chemistry of other elements, and in a short 10 years cyclopentadienyl compounds of nearly all the elements of the periodic table had been prepared. Compounds which have a w bonded sandwich structure are called metallocenes. The research onmetallocenes has contributed exten- sively to an improved understanding of the bonding of transition metals to carbon. Briefly, the structure of ferrocene is that of two planar cyclopentadiene rings which are parallel to each other and have an iron atom sandwiched between them. The two rings are free to rotate about an axis perpendicular to the plane of the rings and equidistant from each of the carbons of the rings. All the carbon-carbon bond distances in the cyclopentadienyl ring are equal, and all carbon-carbon bonds have the same bond order. In this respect the cyclopentadienyl rings resemble the cyclopentadienide anion. The rings are electron rich and have aromatic characteristics. Ferrocene may best be repre- sented as shown in the figure with some net donation of electron den- sity from iron to the rings. Each carbon is symmetrically bonded to the iron. Ferrocene's unique structure imparts certain characteristic properties to this molecule. The rings, with their aromatic character, undergo many of the reactions of benzene - the most important of which is electrophylic substitution. The ferrocene molecule is easily oxidized to the ferricinium ion. 4 The oxidation can be pictured as the removal of an electron from the iron atom thus raising it to a psuedo- plus-three oxidation state. The unusual thermal stability of ferrocene has stimulated research for ferrocene-based, heat-resistant materials. Its symmetrical structure gives it a high vapor pressure and it is readily sublimed. The ferrocenyl group is a strong electron donating group s and it greatly stabilizes an adjacent positive charge. 6,7 Although it stabilizes cationic centers orders of magnitude more than a phenyl group, it is somewhat less effective than a phenyl group in stabilizing adjacent radical and carbonionic centers. m \lJ Fe 8+ //1\ // // I \\ 8- The Ferrocene Molecule A strong attempt has been made to arrange the literature in a functional order useful to the chemist. Necessarily, this attempt is a compromise. For instance, an article reporting the synthesis of acyl ferrocene derivatives may also describe other intermediate com- pounds or subsequent derivatives. It is necessary to choose a specific section under which to include it. in many case_ we n=v= u_== ....... specific paper under two or three headings, but these choices depend on the authors' point-of-view and on limiting the text to an economically reasonable size. Frequently classification of papers into one of the major subdivisions is difficult and the author's viewpoint is followed. Regardless of these obvious shortcomings, we have attempted to pro- vide a document which is easy to use and helpful to the chemist in quickly finding what he needs with a minimum expenditure of time and effort. ,:-',::i-.':',_": " "_- BLANK NOT FILMED. _ • ,.,'_ L..._' * _, • .-_ |" 2". _J_ LITERATURE CITED lo T. J. I4ealy and P. L. Pauson, A NEW TYPE OF ORGANO-IRON COMPOUND, Nature, London, Vol. 168, 1951, p. 1039. G. Wilkinson, M. Rosenblum, M. C. Whiting, and R. B. Woodward, THE STRUCTURE OF IRON BIS-CYCLOPENTADIENYL, American Chemical Society Journal, Vol. 74, 1952, p. 2125. , R. B. Woodward, M. Rosenblum, and M. C. Whiting, THE NEW AROMATIC SYSTEM, American Chemical Society Journal, Vol. 74, 1952, p. 3458. J. Page and G. Wilkinson, THE POLAROGRAPHIC CHEMISTRY OF FERROCENE, RUTHENOCENE AND THE MIDDLE HYDRO- CARBON IONS, American Chemical Society Journal, Vol.