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Universi^ Microrilnris International 300 N. Zeeb Road Ann Arbor, Ml 48106 8403970 Dory, Thomas Sheldon SYNTHESIS AND STRUCTURE OF CVCLOPENTADIENYL TIN(II) COMPOUNDS The University of Oklahoma Ph.D. 1983 University Microfilms I ntern Stionsi SOO N. zeeb Road, Ann Arbor, Ml 48106 PLEASE NOTE: In all cases this material has been Filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V 1. Glossy photographs or pages. 2. Colored illustrations, paper or print_____ 3. Photographs with dark background_____ 4. Illustrations are poor copy______ 5. Pages with black marks, not original copy. 6. Print shows through as there is text on both sides of page. 7. Indistinct, broken or smali print on severai pages ^ 8. Print exceeds margin requirements______ 9. Tightiy bound copy with print lost in spine______ 10. Computer printout pages with indistinct print. 11. Page(s)____________lacking when material received, and not available from school or author. 12. Page(s)____________seem to be missing in numbering only as text follows. 13. Two pages numbered ____________. Text follows. 14. Curling and wrinkled pages______ 15. Other_______________________________________ ______________________________ _ University Microfilms International THE UNIVERSITY OF OKLAHOMA GRADUATE COLLEGE SYNTHESIS AND STRUCTURE OF CYCLOPENTADIENYL TIN(II) COMPOUNDS A DISSERTATION SUBMITTED TO THE GRADUATE FACULTY in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY THOMAS SHELDON DORY Norman, Oklahoma August 1983 SYNTHESIS AND STRUCTURE OF CYCLOPENTADIENYL TIN(II) COMPOUNDS A DISSERTATION APPROVED FOR THE DEPARTMENT OF CHEMISTRY APPROVED BY - ■/I f /. j TO MY PARENTS 111 ACICNOWLEDGMENTS I would like to thank Professor J. J. Zuckerman for his timely remarks and for finding the means for me and others to attend many regional and national American Chemical Society meetings. This proved to be perhaps the single most important contribution to my education at the University. My two trips to Berlin also were helpful to my education. It is my pleasure to thank Professor van der Helm, Drs. C. L. B a m e s , M. B. Hossain and D. R. Powell for their help in the crystal structure work. Valuable discussions with Drs. M. P. Bigwood, R. E. Karl, K. C. Molloy and D. Cunningham made this work easier than it would have been and provided an international flavor to the research group. Also, my fellow graduate students Mr. F. A. K. Nasser, Seik Weng N g , E. Hahn and Dr, W. A. Gust a vs on provided helpful ideas on a wide range of topics. I thank Professors H. B. Abrahamson, N. Fogel, R. ¥. Taylor, R. E. Lehr and Dr. D. L. Tomaja for taking their valuable time to serve on my Dissertation committee and for reading this dissertation. The University of Oklahoma is thanked for providing computer time and the Department of Chemistry for use of all analytical equipment in the iv department. A special thanks to Drs. E. Enwall and T. Karns for assistance in using the ÎIMR and mass spec instruments. I am indebted to all my friends both in the Chemistry Department and outside for making my time in Norman some of my best spent years. V "'The time has come,' the Walrus said, 'To talk of many things : Of shoes— and ships— and sealing wax- Of cabbages— and kings— And why the sea is boiling hot— And whether pigs have wings.'" Lewis Carroll Through the Looking Glass VI ABSTRACT The synthesis of novel organotin(II) compounds was carried out in an attempt to understand the physical and chemical properties in these very reactive systems. Compounds comprising two new classes of organotin (II) complexes were prepared. Two single crystal x-ray data sets were collected with one successfully solved. The reaction of tin (II) chloride with thallium(I) cyclopentadiene salts, TIC^H^X, where X = Cl, Br, I produces a mixture of products instead of the desired Sn(ri®-CgH^X)2 . In the attempt to produce trimethyltin(IV) chlorocyclo- pentadiene from trimethyltin(IV) chloride and chlorocyclo- pentadienylthallium(I), the known compound N-trimethyltin(IV) succinimide was synthesized. Thallium(I) succinimide was produced in the synthesis of chlorocyclopentadienylthallium(I) and reacted with trimethyltin(IV) chloride in preference to chlorocyclopentadienylthallium(I). A new class of divalent tin compounds, stannocenophanes, having the general formula CgH^(CHgCgH^)gSn, were prepared from the ofitho-, mzta- and pa/ia-isomers of the disodium salts of phenylenemethylenedicyclopentadienide and tin(II) chloride. The boron trifluoride adduct of the meta-isomer was synthesized and characterized. vii A second new class of divalent organotin compounds was produced by the reaction of cyclopentadienyltin(II) chloride with the ring-substituted thallium(I) salts TlCgH^R, where R = C(O)CHg, C (0)OCHg, C( 0 )0 CH 2 CH 2 . The products are the first examples of ring-substituted stannocenes, (n^-CgHg)Sn- (n=-CgH^R). The boron trifluoride adduct of stannocene was prepared and its single crystal x-ray structure solved at 138 K. The complex is described by the formula BP^•(n^-CgHg)2 Sn2 *C^HgO. The complex crystallizes in the orthorhombic space group with a = 9.258, b = 13.252, c = 16.437^. The solution was refined to a final R value of 0.0374. Individual [BF^] , (Tl^-CgHg)gSn, [n^-CgHgSn]"*" and THF units are linked together in a three-dimensional lattice. The interactions include fluorine bridging between tetrafluoroborate and stannocene moieties and coordination by THF to the stannocenium cation. Each cyclopentadienyl ring lies along a tin-tin vector to give a three-dimensional network of bridging ri^-CgH^ groups. The boron trifluoride adduct of stannocene was reacted with the molybdenum hydride, HMo(CO)^(n^-CgH^). The compound was characterized by microanalytical analysis, melting point, NMR, ir, Mossbauer and mass spectroscopy. A crystal was grown from solutions of THF and acetone- ethanol, but the x-ray data could not be solved for the structure. The tin(IV) hydride, HSn[Mo(CO)g-n^-Cg(CHg)^]^, viii was synthesized and characterized, IX TABLE OF CONTENTS Chapter Page I. INTRODUCTION 1.1 Historical Background....................... 1 1.2 Stannocene and Its Boron Trifluoride Adduct......................................... 7 1.3 Comments on Stannocenophanes................. H 1.4 Ring Substituted Cyclopentadienes and Reactions................................. 14 1.5 Reactions Involving Transition Metal Hydrides with Tin (II) Compounds.............. 19 II. CRYSTAL AND MOLECULAR STRUCTURE OF THE BORON TRIFLUORIDE ADDUCT OF STANNOCENE 2.1 Introduction................................. 30 2.2 Data Collection.............................. 30 2.3 Structure Determination and Refinement 32 2.4 Description of the Structure.............. 33 2.5 Conclusions................................... 45 III. SYNTHESIS AND CHARACTERIZATION OF N-(TRIMETHYLSTANNYL)SUCCINIMIDE 3.1 Introduction................................. 62 3.2 Synthesis of N-Trimethylstannylsuccinimide. 62 X Chapter Page 3.3 Characterization of N-Trimethyl- stannyleuccinimide............................ 6 6 3.4 Conclusions.................................... 7 3 IV. SYNTHESIS AND CHARACTERIZATION OF STANNOCENES 4.1 Introduction................................... 78 4.2 Synthesis of a,a"-Dicyclopentadienylxylene.. 79 4.3 Synthesis of Disodium (Phenylenedimethylene) dicyclopentadienide........................... 80 4.4 Synthesis of Phenylenedimethylene Bis (n^-Cyclopentadienyl) tin (II).............. 81 4.5 Synthesis of me^a-Phenylenedimethylene Bis[n ^-cyclopentadienyltin(II)]