University Microfilms, a XEROX Company, Ann Arbor, Michigan the SYNTHESES and COORDINATION PROPERTIES of SOME

ELLER, P h i l l i p G ary, 1947- THE SYNTHESES AND COORDINATION PROPERTIES OF SOME 1 , 2 ,3 , 4-TETRAFLU0R0PHENYLPH0SPHINE LIGANDS AND THE CRYSTAL STRUCTURES OF A TRIGONAL PLANAR COPPER COMPLEX AND A TETRAHEDRAL NICKEL NITROSYL COMPLEX. The Ohio State University, Ph.D., 1971 Chemistry, inorganic University Microfilms, A XEROX Company, Ann Arbor, Michigan THE SYNTHESES AND COORDINATION PROPERTIES OF SOME 1 ,2 ,3, fI--TETRAFLUOROPIIEN YLPHOSPHINE LIGANDS AND THE CRYSTAL STRUCTURES OF A TRIGONAL PLANAR COPPER COMPLEX AND A TETRAHEDRAL NICKEL NITROSYL COMPLEX DISSERTATION Presented in F artial Fu3i*illment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Phillip Gary Eller, B.S. •it V e if- -it- The Ohio State University 1971 .Approved^ v V V J .by u j J j MstryU iV » A dviser Department of Chemistry PaJR.Gjy» ■ Aidviser Department of Chemistry PLEASE NOTE: Some pages have indistinct print. Filmed as received. University Microfilms, A Xerox Education Company ACKNOWLEDGMENTS The author wishes to express his deep appreciation to Dr. Devon W. Meek for his invaluable suggestions and encouragement throughout the synthetic and spectral investigations, and in particular for his willingness to permit a large degree of independence to the author in his studies. The author is indebted to his co-adviscr, Dr. P. W. R. Corfieid, for his infinite patience, encouragement, and invaluable suggestions throughout the crystal structural studies. The opportunity to do x’esoarch under two advisers has provided a rich and enjoyable study environment and the coadvisers mutual cooperation is deeply appreciated. The author also wishes to express his appreciation for fellowship support in the form of an NDEA Title IV Fellowship and Lubrizol Industrial Fellowships. Finally, the author acknowledges postdoctoral fellows and fellow graduate students in both Dr. Meek's and Dr. Corfield* s group for many stimulating and enlightening discussions. i i VITA 18 August 1 9 ^ 7 ..........................................Born - New M artinsville, Nest V irg in ia 1967 .................................................................B.S. (Chemistry), West Virginia U n iv e rs ity 1967-1969 ....................................................... NDEA T itle IV Fellow, The Ohio State University, Columbus, Ohio Fall, 1969 ...................................................Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1969-1971 ........................................................ L u b rlz o l I n d u s t r i a l Fellow , D ep art ment of Chemistry, The Ohio State University, Columbus, Ohio PUBLICATIONS ' 'Syntheses of New Tetrafluoroaryl Derivatives of Phosphorous and Sulfur1 1, P. Gary Eller and Devon W. Meek, Journal of Organometallic Chemistry, 22, 63I (1970). ' 'The Crystal Structure of a Trigonal Planar Copper Complex’', P. Gary E ller and P. W. R. Corfic Id, Chemical Communications, IO 5 (l9 7 l)* FIELDS OF STUDY Major Field: Inorganic Chemistry Studies in Coordination Chemistry, Professor Devon W. Meek X-ray Crystallography, Professor P. V/. R. Corfield i i i TABLE OF CONTENTS ACKNOWLEDGMENTS..................................................................................................."... i i VITA ...................................................................................................................................... i i i LIST OF TABLES............................................................................................................... v i i LIST OF ILLUSTRATIONS • ............................................................................................. x i PART ONE - THE SYNTHESES AND COORDINATION PROPERTIES OF SOME 1 ,23 lf“T3TRAFLU0R0PHENYLPH0SPHINE LIGANDS I. INTRODUCTION.......................................................................................................... 1 A. Background B. Steric and Electronic Effects of the Perfluorophenyl Ring C. Previously Studied Coordination Compounds Containing Perfluoro-carbon Ligands D. Fluorine Nuclear Magnetic Resonance Studies II. EXPERIMENTAL......................................................................................................... 28 A. Chemicals B. In stru m e n ta tio n C. Fisnmr Measurements D. Elemental Analyses and Molecular Vfeight Determinations E. Gold Analyses F. Synthesis of Ligands and Intermediates G. Preparation of Coordination Compounds of FSP-CH3 H. Preparation of Coordination Compounds of SP-CII3 I. Preparation of FDP and FTP Complexes J. Miscellaneous Preparations K., Space Group Determination of Ni(FSP-CIT3)2(NCS )2 I I I . RESULTS AND DISCUSSION................................................................................... T9 A. Ligand Synthesis B. C o o rd in atio n Compounds o f FSP-CH3 and SP-CH3 1. N ickel(ll) complexes of FSP-CH3 and SP-CH3 2. Palladium(ll) complexes of FSP-CII3 and SP-CII3 5- Rhodium and irid iu m com plexes o f FSP-CH3 and SP-CH3 If. Gold com plexes o f FSP-CH3 iv C. N ickel(ll) Complexes of FDP D. N ickel(ll) Complexes of FTP E. F19 Nuclear Magnetic Resonance Studies of Dimethylpentafluorophenylphosphine Derivatives and Complexes 1. Background 2. F19 and H1 nmr studies F. F'19 Spectra of 1,2,3, ^-Tetrafluorophenyl Compounds IV. REFERENCES...................................................................................................................223 PART TWO - THE CRYSTAL AND MOLECULAR STRUCTURE OF TRIS- (TRII'ETHYLPHOSPimre SULFIDE) COPPER(I ) PERCHLORATE I. INTRODUCTION ..........................................................................................................237 A. Ter-coordination in Metal Complexes B. Tris(trimethylphosphine sulfide)copper(l) Perchlorate I I . EXPERIMENTAL ..........................................................................................................2kQ A. Instrumentation and Computer Programs B. Preparation of [Cu(SP(CH3)3)3]C10(i. C. Crystal Selection D. Space Group Determination ---- E. Absorption Coefficients F. Determination of Accurate Cell Dimensions for Ccu(sp(ch3)3)3](cio4) G. Intensity Data Collection I I I . DATA PROCESSING, STRUCTURE SOLUTION, AND REFINEMENT.......................253 A. Data Processing and Solution of the Phase Problem B. Structure Refinement; the Disorder Problem IV. DISCUSSION OF THE STRUCTURE OF [Cu(SP(CH3 )3 ) 3 ] ( c i0 4 ) .... 289 V. CONCLUSIONS...............................................................................................................3°6 VI. REFERENCES ............................................................................................................... 31° v PART THESIS - THE CRYSTAL AND MOLECULAR STRUCTURE OF NITRCS YL-1,1 , 1-TRIS (DIET H YLPl ICS PHINO)- ETHANiSNICKEL TETRAFLUOROBORATE I . INTRODUCTION.......................................................................................................... 316 I I . CRYSTAL SELECTION AND PRELIMINARY EXAMINATION, DATA COLLECTION, AND DATA REDUCTION............................................................ J2k A. Preparation of Ni( tep) (NO)bF4 B. Crystal Selection and Space Group Determinations of Ni(tcpJ(NOJ b F^. and Ni(tep)(NO)l C. Determination of Accurate Cell Constants for Ni(tep)(NO)BF4 D. Intensity Data Collection E. Data Reduction I I I . STRUCTURE SOLUTION AND REFINEMENT........................................................ 332 A. Initial Refinements B. Absorption Corrections and Averaging of Equivalent Reflections C. Intermediate Refinements D. Determination of the ’'handedness1' of the Crystal and Examination of the Weighting Scheme E. Final Refinements with the Inclusion of Lagrange M ultipliers IV. DISCUSSION OF THE STRUCTURE OF [N i{tep)(N O )]BF.t ....................... 357 A. Crystal Packing + B. The Geometry in the [Ni(tep)(NO)] Cation C. The Geometry in the Disordered Anion V. CONCLUSIONS.......................................................................................................... 378 VI. REFERENCES ................... ■..................................................................................... 38O vi LIST OF TABLES PART ONE T able Page 1. Representative opphenylene ligands ................................................ 3 2. Selected properties of fluorine, chlorine, and h y d ro g e n .......................................................................................................... 5 3. P31 ninr shifts in pentafluorophenylphosphines .......................... 12 l|-. Comparison of least-squares refined F19 chemical shifts and coupling constants determined in this study with those in reference 226 ................................................................................32 5* F10 chemical shifts and coupling constants in some 1,2,3,^ tetrafluoroaryl compounds .............................................. 85 6. Fluorine 19 chemical shifts in symmetrically disubstituted 1,2-tetrafluoi’obenzene compounds ...........................86 4 7- Molar conductivities and magnetic moments for N i(ll) com plexes o f FSP-CH3 .............................................................................. 99 8. Molar conductivities and magnetic moments for N i(ll) com plexes o f SP-CII3 ..................................................................................100 9- Electronic spectra of Ni(ll) complexes of FSP-CH3 . 101 10. Electronic spectra of ili(ll) complexes of SP-CII3 .... 102 11. The solid state electronic spectra of nickel(ll) th io c y a n a te com plexes o f FSP-CH3 and

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