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Transition Metal Complexes of Dicyanoacetylene Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1971 Transition Metal Complexes of Dicyanoacetylene: a Study of the Reaction Chemistry of Low Valence States of the Transition Metals, Platinum, Palladium, Nickel, Rhodium, and Iridium. Gregory Lloyd Mcclure Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Mcclure, Gregory Lloyd, "Transition Metal Complexes of Dicyanoacetylene: a Study of the Reaction Chemistry of Low Valence States of the Transition Metals, Platinum, Palladium, Nickel, Rhodium, and Iridium." (1971). LSU Historical Dissertations and Theses. 2001. https://digitalcommons.lsu.edu/gradschool_disstheses/2001 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]. 71-29,382 McCLURE, Gregory Lloyd, 1993- TRANSITION METAL COMPLEXES OF DICYANOACETYLENE: A STUDY OF THE REACTION CHEMISTRY OF LOW VALENCE STATES OF THE TRANSITION METALS, PLATINUM, PALLADIUM, NICKEL, RHODIUM, AND IRIDIUM. The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1971 C hem i stry, inorgan ic University Microfilms, A XEROX Company , Ann Arbor. Michigan THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED TRANSITION METAL COMPLEXES OF DICYANOACETYLENE: A Study of the Reaction Chemistry of Low Valence States of the Transition Metals, Platinum, Palladium, Nickel, Rhodium, and Iridium 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 Gregory Lloyd McClure B.A., Rice University, 19^5 May, 1971 ACKNOWLEDGEMENT I would like to express here my appreciation to all of those people who have contributed to my educational advancement, A special thanks is due to the faculty and staff of the Chemistry Department of Louisiana State University, and particularly to Dr. William H. Baddley, who offered me the opportunity to work on this intriguing research pro­ ject, and who patiently guided the course of this work. The writer gratefully acknowledges financial assistance from the Dr. Charles E. Coates Memorial Fund of the Louisiana State University Foundation, donated by George H. Coates, for expenses per­ tinent to the publication of this Doctoral Dissertation. I am particularly indebted to Mr. Ralph Seab, who performed most of the elemental analyses cited herein, Dr, E. E. Green, who as­ sisted in the preparation of the nuclear magnetic resonance spectra, and to Mrs. Lynn DeSille, who typed the manuscript. 11 TABLE OF CONTENTS PAGE ACKNOWLEDGEMENT................................................ il LIST OF TABLES................................................. vli LIST OF FIGURES................................................ vill ABSTRACT....................................................... x I. INTRODUCTION A. Preliminary Remarks and Background Considerations... 1 B, Statement of the Problem............................ II II. A REVIEW OF TRANSITION METAL-ACETYLENE CH01ISTRY........ 1L III. A REVIEW OF DCNA CHEMISTRY A. Physical Properties of DCNA......................... 51 B. Preparative Methods for Dlcyanoacetylene............ $8 C. Reaction Chemistry of DCNA.......................... b2 1. Cycloaddlt Ions.................................. 2. Polymerizations................................. 5. 1 ,2-Addltlona of Inorganic Reagents......... 5l D. Previously Studied Reactions of DCNA with Transition Metals.............................................. 56 IV. EXPERIMENTAL CHEMISTRY OF PLATINUM A. Materials........................................... 59 B. Instruments and Analyses............................ 67 C. Apparatus and Procedure.............. od D. Preparation of Some Platinum Complexes of DCNA..... 09 1. Bis (t ripheny lphosphlne)dicyanoacetyleneplat lnum. t>9 2. Bis(triphenylarsine)dicyanoacetyleneplatlnum.... 70 3. Bis(trlethylphosphlne)dicyanoacetyleneplatlnum.. 71 Lrans-Chloro{dIcyanovinyl)bis(triethylphosphlne)- platlnum(ll).............................. 72 E. Reactions of Some Complexes of the Type Pt(Ph3P)2- (R-C^C-R)........................................... 75 1. Displacement Reactions...................... 77 2. Addition Reaction with Bromine.............. 7^ 3. Reactions with Hydrogen Halides............. 75 111 PAGE F. Addition of Phenyldiazomethane to Pt (Ph3P ^(DCNA) . 81 G. Addition of Bis(triphenylphosphine)platinum(o) to Pt(Ph3P)2( DCNA)................................. 82 H. Reaction of Pt(Ph3P )^(DCNA) with Acetyl or Benzyl Chloride......................................... 82 I. Miscellaneous Reactions of Pt(Ph3P)P(DCNA)....... B3 V. EXPERIMENTAL CHEMISTRY OF PALLADIUM, NICKEL, AND GOLD A. Materials.......................................... 8^4 B. Reactions of Some Palladium(o) Complexes......... BL 1. Reaction of DCNA with Pd(Ph3P)4............... 81* 2. Reaction of FUMN with Pd(Ph3P)4........*...... 86 3. Reaction of Aerylonitrile (ACL) with Pd(Ph3P)4 87 1*. Reaction of Cinnamonitrile with Pd(Ph3P)4 87 9. Reaction of Phenylacetylene with Pd(Ph3P)4.... 88 6. Preparation of Bls{trlphenylphosphlne)dicyano- ace ty lenepal ladiunt from Dicyanoacety lene and Pd (Ph3P ) FUMN)............................. 89 7. Reaction of Dicyanoacetylene with PdClp(PhCN)^ 90 C. Attempted Reaction of DCNA with a Gold(l) Complex, 91 D. Reactions of DCNA with Some Nickel(o) Complexes.,. yl 1. Attempted Reaction of DCNA with Bis(tripheny1- phosphine) ethylenenickel (o)................. 91 2. Attempted Reaction of DCNA with Dicarbonyl- (diphos)nickel(o)........................... 92 VI. EXPERIMENTAL CHEMISTRY OF IRIDIUM AND RHODIUM A. Materials......................................... 9h B. Preparation of Some Dlcyanoacetylene Complexes of Iridium..................................... 9^ 1. Chlorocarbonyl(dicyanoacetylene)bis(tripheny1- phosphlne) iridium .............. 9U 2. Bromocarbonyl(dicyanoacetylene)bis(tripheny1- phosphine) iridium.................... 95 3. Iodocarbony1(dicyanoacetylene)bis(tripheny1- phosphine) iridium..................... 99 k. Isothlocyanatocarbonyl(dlcyanoacetylene)bis- (triphenylphosphine) iridium.......... ^b 5. Chlorocarbonyl(dicyanoacetylene)bis(tripheny1- arsine) iridium........................ 97 6. Chlorobls(dicyanoacetylene)bis(tripheny1- phosphlne) irldlutn..................... 97 7* Dicyanovinyl(carbonyl)(dicyanoacetylene)bis- (tripheny lphosphine) iridium.......... 98 iv PAGE 8. Attempted Reaction of DCNA with Ir(H)CO(Ph3P)3 99 9. Attempted Reaction of DCNA with Ir(h )CO(FUMN)- (Ph3P) ^..................................... 100 10. Reaction of DCNA with Ir(CO)(dlphos)^Cl....... 101 11. Attempted Reaction of DCNA with Ir(dlphosJ^Cl. 101 C. Reactions of Some Iridium Complexes with Fumaro- nitrile........................................... 108 1. Attempted Reaction of FUMN with [Ir(dlphos)^]- C1.......................................... 108 8. Isothlocyanato(carbonyl)fumaronitrileb is- (tripheny lphosphine) Iridium................ lo D. Reactions of DCNA with Some Rhodium Complexes 105 1. Reaction of DCNA with ChlorotrIs(tripheny1- phosphlne )rhodium( I)....................... 10 5 8. Reaction of DCNA with |i, ^-dichlorotetakis- (tripheny lphosphine )dirhodlum( I)........... 10 h 5. Chlorocarbonyldlcyanoacetylenebis(t ripheny1- phosphlne) rhodium........ lOj 1+. Reaction of DCNA with trans-RhCl(CO) ^.(Ph3P). 10b 5. Reaction of DCNA with ti,ti-dichlorotetra- carbony ldirhodiumf I)....................... 107 6. Reaction of DCNA with Iaothlocyanatocarbony1- bis( tripheny lphosphine) rhod ium( I).......... 108 7. Reaction of Some Activated Acetylenes with Chloro(dicarbonyl)triphenylphosphine- rhodium(l).................................. 110 VII. RESULTS OF EXPERIMENTAL INVESTIGATIONS A. Platinum Chemistry............................... 112 B. Palladium Chemistry.............................. Ill* C. Nickel ChemiBtry................................. 115 D. Gold Chemistry................................... 116 E. Rhodium Chemistry................................ 116 F. Iridium Chemistry................................ 117 VIII. DISCUSSION A. Platinum Complexes............................... 119 B. Attempted Reaction of DCNA with a Gold(l) Ccmplex. IU5 C. Reactions of DCNA with Complexes of Palladium and Nickel............................................ v PAGE D. Reactions of Dlcyanoacetylene with Complexes of Rhodium and Iridium............................. 1ST 1. Iridium...................................... 1^7 2. Rhodium...................................... ITT BIBLIOGRAPHY................................................ 195 VITA........................................................* vi LIST OF TABLES TABLE PAGE I. Some Physical Properties of Dlcyanoacetylene...... 52 II. Bond Lengths of Some Linear Molecules............. 5** III, Fundamental Vibrational Frequencies of Dicyano- acetylene....................................... 55 IV. Classical Organic Preparative Route to Dicyano- acetylene............ 59 V. Stability Data for Platinum Complexes of the Type Pt(Activated Acetylene) (pPh^)^................. 120 VI. Thermal Stabilities and Coordinated Acetyienic Stretching Frequencies of some
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