Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1974 Reactions of Sulfur-Dicyanide and Sulfur- Dichlorides With Transition Metal Complexes. Diane Singleton Hamilton Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Hamilton, Diane Singleton, "Reactions of Sulfur-Dicyanide and Sulfur-Dichlorides With Transition Metal Complexes." (1974). LSU Historical Dissertations and Theses. 2730. https://digitalcommons.lsu.edu/gradschool_disstheses/2730 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]. 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Xerox University Microfilms 300 North Zeob Road Ann Arbor, Michigan 4a 105 h'V-\ I i 1 75-14,253 ?, HAMILTON, Diane Singleton, 1947- F REACTIONS OF SULFUR DICYANIDE AND SULFUR : DICHLORIDES WITH TRANSITION METAL COMPLEXES. !. The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1974 Chemistry, Inorganic Xerox University MicrofilmsAnn , Arbor, Michigan 48106 THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. REACTIONS OF SULFUR DICYANIDE AND SULFUR DICHLORIDES WITH TRANSITION METAL COMPLEXES 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 Diane Singleton Hamilton A.A.t Southwest Mississippi Junior College, I967 B.S., Louisiana State University, I97O December, 197^ To Ernie ACKNOWLEDGEMENT The author is deeply grateful to Dr. William H. Baddley for his guidance and encouragement throughout this work. A special thanks is due to my fellow-workers, Mr. William Pitts, Mr. George Tupper, and Mr. pranab Choudhury for their meaningful assistance and suggestions in the laboratory, to Mr. Ralph Seab for his performance of most of the elemental analyses reported herein, to Mr. George Sexton for his maintenance of the instruments used in the re­ search, to Mrs. Lynn DeSille for her efficient typing of the manuscript, and to Dr. Duane Wolcott for his skillful drawing of the figures and structures. The author gratefully acknowledges the Dr. Charles E. Coates Memorial Fund of the Louisiana State University Foundation donated by George H. Coates, for expenses incurred in the preparation of this Dissertation. For financial assistance from the Department of Chemistry, Louisiana State University-Baton Rouge, in the form of Teaching and Research Asslstantshlps I am particularly grateful. Finally, I want to thank my parents, Frank and Marguerite Singleton, and my husband, Ernie, for their encouragement and moral support which were essential to my attaining this goal. iii TABLE OF CONTENTS PAGE ACKNOWLEDGMENT............................................. 111 LIST OF TABLES.............................................. vii LIST OF FIGURES..................................... viii LIST OF ABBREVIATIONS....................................... ABSTRACT.................................................... x I. INTRODUCTION......................................... 1 A. Preliminary Remarks............................... I B. Review of Metal Complexes Containing SR and SR2 Ligands.................................. 3 C. Statement of the Problem......................... 7 D. Chemistry of Sulfur Dicyanide, Sulfur Dichlorlde, and Dlsulfur Dichloride................ 8 II. EXPERIMENTAL - GENERAL................................ 20 A. Materials................ 20 B. Instrumentation......... 21 C. General Preparative and Purification Techniques.... 22 III. EXPERIMENTAL - SULFUR DICYANIDE REACTIONS.... 2k A. Reactions of trans-IrX(CO)Le [L = PPh3 , X * Cl, Br, C(CN)3 , NCS; L - FMePh2, AsPh3 , X “ Cl] with s(CN)2........ 2k 1. Preparation and Characterization of the Linkage Isomers IrCl(CN)(SCN)(C0)(PPh3 )2 and IrCl(CN)(NCs)(C0)(PPh3 )2................ 2k 2. Preparation and Characterization of the Linkage Isomers IrCl(CN)(SCN) (C0)(PMePh2) 2 and IrCl(CN) (NCS) (CO) (PMePh2) 2................ 25 3. Preparation and Characterization of the Linkage Isomers irBr(CN)(SCN) (CO)(PPh3 )2 and IrBr (CN)(NCS)(CO) (PPh3 ) 2.................. 26 4. Preparation and Characterization of Ir[C(CN)3](CN)(sCN)(C0)(PPh3)2................ 27 5. Preparation and Characterization of the Linkage Isomers Ir(NCS)(CN)(SCN)(C0)(PPh3)2 and Ir(NCS)2(CN)(CO)(PPh3)2................... 27 iv PAGE 6. Preparation and Characterization of the Linkage Isomers IrCl(CN)(SCN)(CO)(AsPh3)2 and IrCi(CN)(NCS)(CO)(AsPh3 )2............... 28 B. Reaction of IrH(CO)(PPh3 )3 and s(CN)2 ..... ........ 29 C. Reaction of IrH(CO)2 (PPh3 )2 and s(CN)2 ............. 30 D. Reaction of trans-IrClN2 (PPh3 )2 and s(CN)2 ......... 31 E. Reaction of tran£-RhX(CO)(PPh3)2 (X s Cl, Br) and S(CN)2 .......... ............................... 32 1. Preparation and Characterization of the Linkage Isomers RhCl(CN)(SCN)(CO)(PPh3 )2 and RhCl(CN) (NCS) (CO) (PPh3)2.................. 32 2. Preparation and Characterization of RhBr(CN) (SCN) (CO) (PPh3 )2 ....................... 32 F. Reaction of BhCi(PPh3 )3 and s(CN)2 ................. 33 G. Reaction of Pt(pph3)4 and S(CN)2.................. 34 H. Reaction of Pt(Co)2 (PPh3 )2 and S(CN)2 .............. 34 I. Attempted Reaction of AuCl(pph3) and S(CN)2........ 35 IV. RESULTS OF SULFUR DICYANIDE REACTIONS................. 37 V. DISCUSSION OF SULFUR DICYANIDE REACTIONS.............. 41 A. Iridium Chemistry................................. 41 B. Rhodium Chemistry................................. 70 C. Platinum Chemistry................................ jh D. Gold Chemistry.................................... 82 VI. EXPERIMENTAL - SULFUR DICHLORIDE AND DISULFUR DICHLORIDE REACTIONS.................................. 83 A. Reactions of trans-IrX(CO)(PPh3)2 (X = Cl, Br, NCS) with SC12................................ 83 1. Preparation and Characterization of IrCl2(sCl)(CO)(PPh3 )2 ......... 83 2. Preparation and Characterization of IrBrCl (SCI) (CO) ( PPh3 ) ........................ 84 3 . Preparation and Characterization of Ir(NCS)Cl(SCl)(CO) (PPh3) 2..................... 84 B. Reaction of [lr(diphos)2]Cl and SC12.... ......... 85 C. Reaction of _trans-RhCl(CO) (PPh3 )2 and SC12 ......... 86 v PAGE D. Reaction of Pt(pph3 ) 4 and SC12 ............ 86 E. Reaction of Pt(C0)2(PPh3)2 and SC12.............. 87 F. Reactions of trans-IrX(CO)(PPh3) 2 (X = Cl, Br, NCS) with S^Ci^ and S2Br2 ......... .......... 88 1. Preparation and Characterization of lrCl(CO)(PPh3 )2*SsCls........................ 88 2. Reaction of IrCl(CO)(PPh3 )2 with S2Br2....... 89 3 . Preparation and Characterization of IrBr(CO) (PPh3 )2 'S2Cl2........................ 90 4. Preparation and Characterization of Ir(NCS)(CO)(PPh3 )2*S2Cl2.................... 91 G. Reaction of [lr(diphos)2]Cl and S2C12.......... 91 H. Reaction of RhCl(CO) (PPh3 )2 and S^ l e ............. 92 I. Reaction of Pt(PPh3 ) 4 and S2C12............ 1..... 9? J. Reaction of Pt(C0)2(PPh3 )2 and S2C12....... 93 VII. RESULTS OF SULFUR DICHLORIDE AND DISULFUR DICHLORIDE REACTIONS....... 95 VIII. DISCUSSION OF SULFUR DICHLORIDE AND DISULFUR DICHLORIDE REACTIONS.................................. 98 A. General Reactivity of Sulfur Halides.............. 98 B. Sulfur Dlchlorlde,Reactions... .•.............. 99 1. Iridium Chemistry............................. 99 2. Rhodium