Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1958 Ring Size and Reactivity of Cyclic Olefins: Complexation With Aqueous Silver Ion and With Molecular Iodine. Jerome Robert Olechowski Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Olechowski, Jerome Robert, "Ring Size and Reactivity of Cyclic Olefins: Complexation With Aqueous Silver Ion and With Molecular Iodine." (1958). LSU Historical Dissertations and Theses. 452. https://digitalcommons.lsu.edu/gradschool_disstheses/452 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. RING SIZE AND REACTIVITY OF CYCLIC OLEFINS: COMPLEXATION WITH AQUEOUS SILVER ION AND WITH MOLECULAR IODINE A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Jerome Robert Olechowski B.S., Canlsius College, 1952 M.S., The Pennsylvania State University, 1955 January, 1958 ACKNOWLEDGEMENT The author wishes to thank Dr. James G. Traynham, who suggested and guided this investigation. The author wishes to acknowledge the financial aid from the Celanese Corporation of America and from the Petroleum Research Fund of the American Chemical Society, in the form of fellowships. A person who has never written a dissertation may wonder why authors so frequently acknowledge the patience and understanding of their wives. Many of the hours which went into the working of this dissertation were taken from the evening hours which would otherwise have been spent with my family or from time which might have been spent doing the innumerable odd jobs which seem to arise around a household. My wife has not only borne this with patience and understanding, but has given me a wealth of valuable advice and encouragement. To her go my most grateful thanks. There are others who in some small way have aided in the completion of this work and Instead of naming all of them, I would like to express my thanks. Mr. William S. Weems, a capable assistant, was a tre­ mendous help to me during the summer of 1957* ii TABLE OF CONTENTS PAGE I. INTRODUCTION 1 II. METAL - ION OLEFIN COMPLEXES 3 III. IODINE - OLEFIN COMPLEXES 7 IV. EXPERIMENTAL 13 V. INTERPRETATION OF EXPERIMENTAL RESULTS 12 VI. CONCLUSION 86 VII. SELECTED BIBLIOGRAPHY 88 VIII. VITA 92 111 LIST OF TABLES TABLE PAGE I Wave Lengths Used for Olefin Analysis in Near-Infrared Region. Silver Ion- 01 e fin Complexation 30 II Equilibrium Data for Complex Forma­ tion. Cyclopentene-Silver Ion 31 III Equilibrium Data for Complex Forma­ tion. Cyclohexene-Silver Ion 32 IV Equilibrium Data for Complex Forma­ tion. Cycloheptene-Silver Ion 33 V Equilibrium Data for Complex Forma­ tion. cls-Cycloflctene 34 VI Equilibrium Data for Complex Forma­ tion. Methylenecyclobutane-Silver Ion 35 VII Equilibrium Data for Complex Forma­ tion. Methyleneeyelopentane-Silver Ion 36 VIII Equilibrium Data for Complex Forma­ tion . Methylenecyclohexane-Silver Ion 37 IX Equilibrium Data for Complex Forma­ tion. Methylenecycloheptane-Silver Ion 38 X Equilibrium Data for Complex Forma­ tion . Bicyclo[2.2.1]heptene-Silver Ion 39 XI Equilibrium Data for Complex Forma­ tion . Bicyclo[2.2.2]octene-Silver Ion 40 XII Equilibrium Data for Complex Forma­ tion . Bicyclo[2.2.1]hepta-2}5-diene Silver Ion 41 Iv LIST OF TABLES (Continued) TABLE PAGE XIII Thermodynamic Bata for the Reaction of Eleven Cyclic Olefins with Aqueous Silver Ion A2 XIV Representative Bata for the Betermi- natlon of the Cyclopentene-Iodine Spectroscopic Equilibrium Constant 60 XV Representative Bata for the Determi- nation of the Cyclohexene-Iodine Spectroscopic Equilibrium Constant 61 XVI Representative Bata for the Determi- nation of the Cycloheptene-Iodine Spectroscopic Equilibrium Constant 62 XVII Representative Bata for the Determi- nation of the cls-Cyclo8ctene-Iodlne Spectroscopic Equilibrium Constant 65 XVIII Representative Bata for the Determi- nation of the Methylenecyclobutane- Iodine Spectroscopic Equilibrium 6A XIX Representative Bata for the Determi- nation of the Methylenecyclopentane- Iodine Spectroscopic Equilibrium 65 Constant XX Representative Bata for the Determi- nation of the Methylenecyclohexane- lodine Spectroscopic Equilibrium 66 Constant XXI Representative Bata for the Determi­ nation of the Methylenecycloheptane- Iodine Spectroscopic Equilibrium 67 Constant XXII Extinction Coefficients for Olefin- Iodine Complexes at the Wave Length of Maximum Absorption of the Complex 68 v LIST OP TABLES (Continued) TABLE PAGE XXIII Equilibrium Data for Complex Forma­ tion. Olefin-Molecular Iodine 69 XXIV Thermodynamic Data for Complex Forma­ tion. Olefin-Molecular Iodine 70 XXV Order of Complexation of Cyclic Ole­ fins with Aqueous Silver Ion and Molecular1 Iodine 71 XXVI Variation of Keq o with Silver Ion Concentration for Biallyl and 2,5- Dimethyl-1,5-butadiene 77 vi LIST OF FIGURES FIGURE PAGE 1 Calibration Plot of Concentration of Cyclopentene versus Optical Density 44 2 Calibration Plot of Concentration of Cyclohexene versus Optical Density 45 3 Calibration Plot of Concentration of Cycloheptene versus Optical Density 46 4 Calibration Plot of Concentration of eis-Cyclodctene versus Optical Density 47 5 Calibration Plot of Concentration of Methyleneeyelobutane versus Optical Density 48 6 Calibration Plot of Concentration of Methyleneeyclopentane versus Optical Density 49 7 Calibration Plot of Concentration of Methyleneeyelohexane versus Optical Density 50 8 Calibration Plot of Concentration of Methylenecycloheptane versus Optical Density 51 9 Calibration Plot of Concentration of Bicyclo[2.2.ljheptene versus Optical Density 52 10 Calibration Plot of Concentration of BIcyclo[2.2.2]octene versus Optical Density 53 11 Calibration Plot of Concentration of Bicyclo[2.2.l]hepta-2J5-diene versus Optical Density 5^ 12 Linear Relationship of AH° and AS° for the Olefln-Iodlne Complexes 85 vli ABSTRACT The effect of ring size on the reactivity of cyclic olefins was investigated through study of the olefin com­ plexes with aqueous silver ion and with molecular iodine. The close resemblance between structures postulated for pi-complexes derived from olefins and for the transition states or intermediates in addition reactions suggested that studies of the complexes may be helpful in under­ standing the details of the addition reaction. The olefins selected for use as donor species were cycloalkenes (ring sizes C5 through Cs)^ methylenecyclo- alkanes (ring sizes C4 through C7 ), bicycloheptene, bi- cyclo6ctene and bicycloheptadiene. The silver ion complexes were studied by distribution of olefin between carbon tetrachloride and aqueous silver nitrate, and formation constants and thermodynamic func­ tions for the reaction 01efin(co:u) + Ag|H20) 5 Complex^) were evaluated for each olefin studied. It was found that the formation constants for the silver ion complexes of the cycloalkenes and bicycloalkenes are in the same order as the estimated relative strains in the olefins. The order observed was C5 )> C7 )> C6 Cs and bicyclo[2.2.1] viii heptene )>bicyclo[2.2.2]octene. At 25° the ratio of the largest (bicyclo[2.2.1]heptene) and smallest (cis-cyclo- 6ctene) formation constants among these compounds is 55.1. Small variations in the entropy of reaction were found, although the enthalpy factor appears to reflect the pre­ dominant effect. The formation constants for the silver ion complexes of the methylenecycloalkanes show less dependence on ring size. The order observed was C4 )> C7 )> C5 )> C6 . The ratio of the largest and the smallest formation constants in this series was 1.5:1. The AH° terms are less favor­ able in this series than those of the more extensively coraplexed cycloalkenes, but the AS° terms are signifi­ cantly more favorable by approximately 10 entropy units. Bicycloheptadiene was found to form predominately or exclusively a 1:1 complex with aqueous silver ion, in con­ trast with other dienes which are found to form both 1:1 and 1:2 complexes. There was no apparent change in K „ eq* with changes in silver nitrate concentration, which is indicative of the absence of any 1:2 complex. Analysis of a solid complex of bicycloheptadiene-silver nitrate formed in the absence of solvent also indicated formation of a 1:1 complex. ix Formation constants and thermodynamic functions for the interaction of two series of cyclodlefins with iodine in 2,2, ■ trimethylpentane were determined by spectrophoto- metric methods. The formation constants for the olefln-iodine complexes exhibit less dependence upon ring size than do those for the silver-eycloalkene complexes. The orders of formation con­ stants are Cycloalkenes: CQ > C7 > C5 > Ca Methylenecycloalkanes: C6 > C4 > C7 > C5 The small differences which do occur among the forma­ tion constants for the iodine complexes with the cyclo­ alkenes are in the opposite order to those for the silver ion complexes. The lack of parallel trends among the sil­ ver ion complexes and the iodine complexes implied that there is the possibility of a subtle difference in structure of the two types of complexes studied. x