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Xerox University Microfilms, Ann Arbor, M Ichigan 48106 I I I 77-2394 EDWARDS, Robert Charles, 1949- SYNTHESES AND CHARACTERIZATION OF CHROMIUM COMPLEXES WITH TETRAAZA MACROCYCLIC LIGANDS. The Ohio State University, Ph.D., 1976 Chemistry, inorganic Xerox University Microfilms, Ann Arbor, Michigan 48106 SYNTHESES AND CHARACTERIZATION OF CHROMIUM COMPLEXES WITH TETRAAZA MACROCYCLIC LIGANDS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Robert Charles Edwards, B.S. The Ohio State University 1976 Reading Committee: Approved by Professor Daryle H. Busch Professor Devon W. Meek Professor Eugene P. Schram Advised Department of Chemistry To Debra and Marie & # 5J: aj: % # # # ACKNOWLEDGEMENTS I would like to acknowledge the help given to me by fellow graduate students, post-doctoral fellows in Dr. Busch's group, and the staff in the Department of Chemistry. I want to especially thank Professor Daryle H„ Busch for his guidance and understanding,, iii CURRICULUM VITAE March 2, 1949. ................ ... ..................................................... Born, Marion, Ohio 1971 .................................................. ................................................ B .S., Heidelberg College Tiffin, Ohio 1971-1974. ....................................................................................... Teaching Associate, Dept, of Chemistry, The Ohio State University, Columbus, Ohio 1974-197 5 ................................................................................. Allied-Chemical Fellow The Ohio State University, Columbus, Ohio 1975-1976 . ................... .............. Research Associate, Dept, of Chemistry, The Ohio State University, Columbus, Ohio 1976 ...................................................................................................Ph. D ., The Ohio State University, Columbus, Ohio PUBLICATIONS Robert C. Edwards and Daryle H. Busch, "Synthesis and Properties of Chromium(I), (III), and (IV) Complexes", American Chemical Society Centennial Meeting, New York City, New York, April, 1976, Abstr. INOR-153. FIELD OF STUDY Major Field: Chemistry Specialization—Inorganic Coordination Chemistry Professor Daryle H. Busch, adviser iv TABLE OF CONTENTS Page. Acknowledgements ............................................................ ...... ..... .......... iii Curriculum Vitae. ........................ ...... ........ ..... .iv List of Tables ..............................................................................................................................vii List of Figures ......................................................................................................................... x Introduction, ........................ 1 Experimental. ............... .19 P hysical ^Measurements......co.o....... .. .. 0. 00. 0. .0. 00........ 19 S yntheses .............................................................................................................................. 21 Results and Discussion. ........... 37 Preparation of [Cr(Me 2[l4]tetraenatoN 4)(py) 2]PFG, [Cr(Me2[i5 ]- tetraenatoN4) (py) 2]PFG> [Cr(Me2[ l6]tetraenatoN 4)(py) 2]PFG, and [Cr(M e4[l4]tetraenatoN 4)(py) 2]PF6o ........................ 37 Preparation of [Cr(Me 2[Z]tetraenatoN 4)(L)2]PF 6 (Z = 14, 15, or 16) and [Cr(Me4[l4]tetraenatoN 4)(L)2]PFG (L = dimethylformamide, 1-methylimidazole, thiocyanate, or cyanide). ................................40 Characterization of [Cr(Me 2[Z]tetraenatoN 4)(L)2jPFG (Z = 14, 15, or 16) and [Cr(Me4[l4]tetraenatoN 4)(L)2]PFG (L = pyridine, dimethylforma­ mide, and 1-methylimidazole) ....................................................... 43 Characterization of Cr(Me 2[Z]tetraenatoN 4)(NCS)(py), Cr(Me 4[l4]- tetraenatoN 4)(NCS)(py), and Cr(Me 2[Z]tetraenatoN4)CN (Z = 14, 15, o r 1 6 ). ............. 57 Oxidation and Other Reactions of the Chromium!HI) Complexes ............... .63 Preparation of Cr(Me 2[Z]tetraenatoN 4)(CGH5)(py) (Z = 14, 15, or 16) and Cr(Me2[14]tetraenatoN4) (L)(py) (L = Me or n-Bu) 67 Characterization of Cr(Me 2[Z]tetraenatoN 4)(C6H5)(py) (Z = 14, 15, or 16) and Cr(Me 2[l4]tetraenatoN 4)(L)(py) (L = CH 3 or n-B u) ......................... 68 Electronic Spectra of the Chromium!HI) Complexes ........ .................... .75 Electrochemistry of the Chromium(III) Complexes. ............. 86 ESR Spectra of the Chromium(IU) Complexes. ............. 91 Preparation of [Cr(Me 2[l4]tetraenatoN 4) (CGH5)]X (X = I or SCN) ...................100 v TABLE OF CONTENTS Page Characterization of [Cr(Me 2[i4 ]tetraenatoN 4)(C 6H5)]X (X = I and SCN) ............................................... io i Preparation of Cr(Me 2[l4]tetraenatoN 4)(NO) and [Cr(Me6[i4]- 4, il-dieneN 4)(NO)(N02)]PFG.................... ........... ................ 112 Characterization of Cr(Me 2[i4]tetraenatoN 4)(NO) and [Cr(Mee[i4j4, ll-dieneN 4)(N 0)(N 02)]P F s.................... 113 Syntheses and Characterization of Chromium(Il) and (III) Complexes with MeG[l4]4, ll-dieneN4„ ....................... „ ...............123 Preparation of the Chromium (II) and Chromium(III) Complexes 0 ...........123 Characterization of the Chromium(H) and Chromium(IU) C omplexe s . ........................................................................................................................124 AppendlXo .... ...... •o...oao....«ooo...«o*.......a..aoo.o..e. ........ 133 BeferenCeSo 138 vi LIST OF TABLES Page Table 1. Analytical Data for the Complexes, [Cr(Me [ZjtetraenatoN^- (L)2]PF 6 ................................................................................*...... ...................... 44 Table 2. Selected Infrared Absorptions of the Complexes, [Cr(Me [ZjtetraenatoN^lL^ ]PFG ......: ............................... 48 Table 3. Physical Properties of the Complexes, [Cr(Me [ZJtetraenato- N4)(L)2]P F 6. ............................................. * 49 Table 4. Temperature Dependence of the Magnetic Susceptibility of [Cr(Me2{44]tetraenatoN4)(py)2]PF6o 51 Table 5. Temperature Dependence of the Magnetic Susceptibility of [C r (Me2115] te tr aenatoN4) (py) 2] PF 6...............................................................................52 Table 6. Temperature Dependence of the Magnetic Susceptibility of [Cr(M e2[ l6]tetraenatoN 4)(py) 2]PFG...............................................................................53 Table 7. Temperature Dependence of the Magnetic Susceptibility of [Cr(Me4[l4]tetraenatoN 4)(py)2]PFg ........... 54 Table 8 . Magnetic Moments and Weiss Constants Calculated from the Variable Temperature Magnetic Susceptibility Data of the Bis- physical Complexes ...................... 56 Table 9. Analytical Data for the Complexes, Cr(Me [ZjtetraenatoN^- (A)(B). .......................................... ? .......................................... 58 Table 10. Selected Infrared Absorption Bands of the Complexes, Cr(Me [Z]tetraenatoN 4)(A )(B ). .................... 61 x Table 11. Physical Properties of the Complexes, Cr(Me [Zjtetraenato- N4)(A)(B)........................................................................................X. .....................................62 Table 12. Analytical Data for the Complexes with Aryl and Alkyl Ligands... 69 vii Page Table 13. Selected Infrared Absorptions for the Complexes with Aryl and Alkyl Ligands................................................................. ..................................... 72 Table 14. Physical Properties of the Complexes with Alkyl and Aryl L ig a n d s. ........................... 74 Table 15. Comparison of Calculated and Observed Spectral Band Positions of Chromium (HI)—Ethylene diamine Complexes. „.............78 Table 16. Electronic Spectral Data for Chromium(HI) Complexes with; the Ligands Me 6[i4]aneN 4 and Me6[i4]4, ll-dieneN 4 .................79 Table 17. Electronic Spectral Data for the Complexes, [Cr(Me [Z]- tetraenatoN 4)(L)2]PF 6........................................................................... X.........................80 Table 18. Electronic Spectral Data for the Complexes, Cr(Me [Z]- tetraenatoN ^ (A) (B) .................................................... .X. ..........................81 Table 19. Electronic Spectral Data for the Complexes, Cr(Me 2[Z]- tetraenatoN 4) (R) (py). ........................................ 82 Table 20. Electrochemical Data for the Complexes, [Cr(Me [Z]- tetraenatoN 4) (L) 2]P F e............... 87 Table 21. Electrochemical Data for the Complexes, Cr(Mex[Z]- tetraenatoN^ (A) (B) ...................................................................................88 Table 22. Electrochemical Data for the Complexes, Cr(Me 2[Z]- tetraenatoN4) (R) (py) ........... 89 Table 23. Physical Properties of the Chromium(IV) Complexes. .................108 Table 24. Electronic Spectral Data for the Chromium(IV) Complexes. ..........108 Table 25. Analytical Data for the Chromium (I) Nitrosyl Complexes ................116 Table 26. Physical Properties of the Chromium(l) Nitrosyl Complexes.... 116 Table 27. Electronic Spectral Data for the Chromium(I) Nitrosyl C o m p lex es ............................. 116 v iii Page Table 28. Analytical Data for the Chromium(II) Complexes with Me6[l4]4, ll-dieneN 4 . ..................................................................................................... 125 Table 29. Physical Properties of the Complexes with Me 6[l4]4, ii-d ie n e N 4. 126 Table 30. Electrochemical Data for the Cliromium(Il) Complexes .........................127 Table 31. Electronic Spectral Data for the
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