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Preparation and Properties of Tetrachlorophosphonium

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Preparation and Properties of Tetrachlorophosphonium This dissertation has been microfilmed exactly as received 66-1851 WALTHER, James Fletcher, 1938- PREPARATION AND PROPERTIES OF T E TRAC HLOROPHOSPHONIUM TETRACHLORODIFLUOROPHOSPHATE. The Ohio State University, Ph.D., 1965 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan PREPARATION AND PROPERTIES OP TETRACHLOROPHOSPHONIUH TKTRACHLORGDIFLUQROPHOSPHATE DISSERTATION Presented In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy In the Graduate School of The Ohio State University BSP James Fletcher Walther, B.A.* M.Sc* The Ohio State University 1965 Department of Chemistry ACKHCMI2DGMENTS I wish to express ngr sincerest gratitude to my adviser* Or. Sheldon Q. Shore* Tor suggesting this very interesting and perplexing research problem. I am dearly grateful to ay wife* Kay* for her faithful assistance in preparing this dissertation and for her enduring interest and enthusiasm in my work. Also* I want to express my appreciation to the Chemistry Department of The Ohio State University for its financial assist­ ance through various teaching assistantships and summer fellow­ ships. ii VITA August *** 1 9 3 8 ........... Born* St* Louis* Missouri i960 ••••••••• ••• B*A** Central Methodist College* Fayette* Missouri 1960-1963 ....................... Teaching Assistant* Department of Chemistry* The Ohio State University* Columbus* Ohio 1963-196**................... Teaching Assistant* Graduate level* Inorganic Division* Department of Chemistry The Ohio State University* Columbus* (Alio 196*4—1965 ............... Technical Assistant* Department of Chemistry* The Ohio State University* Columbus* Ohio iii CONTENTS Page ACKNOWLEDGMENTS ........................................ 11 VITA ................................................. Ill TABLES................................................ v ILLUSTRATIONS . , . .................................. vi I. INTRODUCTION .................................... 1 II. STATEMENT OF PROBLEM ............................. 10 III. EXPERIMENTAL .................................... 15 A. Apparatus and Experimental Technique ....... 15 B. Reagents 33 C. Chemical Analysis ................... 4 0 D. Spectroscopic Analysis ..................... 45 E. Conductance Measurements .............. 50 IV. DISCUSSION OF RESULTS ............................ 52 A. Preparation of Ionic PCl^F by ftrrolysis of [PClZf]+[PF6] - ............... 52 B. Preparation of Ionic PCl^F by Direct Fluorination of PCl<j............... $6 C. Solution Properties of Ionic PCI^F . 81 D. Attempts to Obtain Nuclear Magnetic Resonance Spectra ......................... 93 E. Fluorination of PCl^ with AgF ....... 94 V. S U M M A R Y ......................................... 100 BIBLIOGRAPHY .......................................... 103 iv TABLES Table Page 1* Physical Properties of Phosphorus(V) Chlorofluorid.es . 9 2. Chemical Analysis Data for Ionic PClnF Made from Pyrolysis of [PClit3+[PF^]” ............... 5^ 3* Infrared Absorption Frequencies of Ionic PCI4 F • • • 63 1*. Infrared Absorption Frequencies of Pure [p c i ^]+ [p f 6 ]- . ............................. 61* 5 . X-ray Powder Diffraction,Data for Ionic PCl^F and Pure [FC1^3 [ E F ^ ] * ................. 76 6, Apparent Molecular Weight of Ionic PCl^F in Nitrobenzene by Freezing-Point D e p r e s s i o n ............. 82 ?• Conductance Data For Ionic PCl^F in Nitrobenzene Solutions ....................... 81* 8* Infrared Absorption Frequencies of Ionic PCljifF in Nitrobenzene ............... 87 v ILLUSTRATIONS Figure Page 1* Apparatus for Pyrolyzing 18 2. Apparatus for Direct Fluorination of PCl^ with AsF3 ................................ 22 3# Powder-Dropping Device ............................ 28 4. Assembled Cryoscopy Apparatus .................... 30 5* Apparatus for Filtering Aqueous AgF Solutions . 3? 6 . Apparatus for Evaporating Aqueous AgF Solutions • . • 38 7* Apparatus for Base Hydrolysis of Solid Phosphorus Halides ............................ 4-1 8 . Infrared Cell for Corrosive Liquids ............. 46 9* Apparatus for Preparing N.M.R. Sample Solutions . 49 10. Infrared Spectrum of Ionic PCI. F by Fluorination of PCl^ with AsF^ in ASCI3 4 ..................... 60 11# Infrared Spectrum of Ionic PCl^F by Pyrolysis of [PC1^]+[PF6]- Sample 2. 60 12. Infrared Spectrum of Pure [PC1^]+[PF^]" (Pressed Pellet) ............................. 6l 13* Infrared Spectrum of Pure [PCI. ]+ [PFA 3" (Nujol M u l l ) .............. 61 14* Infrared Spectrum of Phosphorus Pentachloride t [PClif]T;PCl6]“ (Pressed Pellet) ................. 62 15* Infrared Spectrum of Phosphorus Pentachloride1 [PC14 ]+[PC16]" (Nujol Mull) ..................... 62 16 . Infrared Spectrum of POCl^ in N u j o l .............. 66 17. Infrared Spectrum of Phosphorus Pentachloride Adulterated with P O C l ^ ........................ 66 vi ILLUSTRATIONS (Cont'd.) Figure 18. Infrared Spectrum of Sublimation Condensate from Purification of Ionic PCl^F ......... • • • • 19* Infrared Spectrum of Ionic PCl^F Prepared by Fluorination of PCl^ with AsF- in Nonpolar Solvents ...... ............... • 20* Graphical Comparison of 6-Values of Ionic PCl^F Samples with Values Reported by Kolditz ....... 21. Infrared Spectrum of a Saturated Solution of Ionic PCljjF in Nitrobenzene ............... 22. Infrared Spectrum of a Saturated Solution of Ionic FCI4.F in Acetonitrile ................... 2 3 . Infrared Spectra of a Solution of Ionic PCl^F in Anhydrous Acetic Acid...................... 2k. Infrared Spectra of Pure Anhydrous Acetic Acid . • ♦ 2$. Infrared Spectrum of Acetyl Chloride in Anhydrous Acetic Acid ...................... 26. Infrared Spectrum of Product from Reaction between AgF and PCl^ in CHjjC^ ................. 27* Infrared Spectrum of Product from Reaction between AgF and PCl^ in Benzene I. INTRODUCTION Phosphorus is one of several non-metalllc elements known to exhibit a coordination number of six toward covalently bonded sub­ stituents • An excellent example of this kind of compound is phos­ phorus pentachloride. This material in its normal crystalline state consists of the complex ions [PCl^J^PCl^]” arranged in a distorted cesium chloride type lattice (1) • For the purpose of later discussions» the dualistic nature of this material should be emphasised. In contrast to the ionic character of its solid state> the composition of its liquid (2) and gaseous (3) states has been interpreted in terms of PCl^ trigonal bipyramidal molecules. But* the point of interest to this discussion is the octahedral hexachlorophosphate anion in which phosphorus had increased its coordination sphere to accomodate six substituents. Although a wide variety of compounds are known in which phosphorus has a coordination number of six» the actual number of compounds is not very large. A convenient approach to discussing these materials is to consider them all derivatives of phosphorus pentachloride. The various compounds can be placed in one of several classes according to their basic structures. Class A .— Addition complexes of molecular phosphorus penta­ chloride or its molecular derivatives— L #FClaX^_t. Class B .— Replacement of the complex [PC1^]+ cation of ionic phosphorus pentachloride by another cation— M’^tPCl^]*'. 1 2 Class C .— Replacement of the [FCl^]* cation by another cation and successive replacement of chlorine atoms on the complex [P&^l anion by other atoms or radicals— ^ [ P C l ^ X ^ ^ 3^. Class D .— Successive replacement of the chlorine atoms on the [PC16]“ anion by other atoms or radicals— [PCl^]+[PClaX ^ ^ ] “ . Class A compounds include a rather extensive list of addition complexes of phosphorus pentafluoride. Phosphorus pentafluorlde has been shewn to be a strong Levis acid forming one-to-one complexes with amines* ethers* nitriles* sulfoxides* and many other organic bases (4-)* Pyridine complexes of the molecular species PCl^ (5)* PCl^F* PCl^Fg* and PCI2F^ (6) have been described* The older of Levis acid strengths toward pyridine is as expected; FCl^Fg > FCl^F > PC15 (?)* The PClgFj complex has the formula 3py*2PCl2F^* The struc­ ture of this complex is hard to visualize unless a seven-coordinate phosphorus species is assumed* A carbon tetrachloride complex of phosphorus pentachloride having the formula CCl^*2PC1^ has been re­ ported (8). The complex vas formed as a precipitate upon cooling a saturated solution of phosphorus pentachloride in carbon tetrachloride* This complex might involve ionic phosphorus pentachloride instead of the molecular form* such as (CC1^*FC1^ 3+[PC1^ ] % in vhich cationic phosphorus acts as an acceptor for non-bonded p electrons on the carbon tetrachloride molecule* A biphosphorus ccmplex having a bridge type bond involving the chlorines on carbon tetrachloride is another pos­ sibility. The latter is more likely because no evidence has been found for ion pair formation of phosphorus pentachloride in carbon tetrachloride solutions (9)* The species PBr^*2CCl^ vas also 3 reported (8*10). Two other species * PCl^BryCCl^ and FCl^Br^#2CCl^> were isolated from PCl^-Br^-CCl^ systems (11). Whether or not six coordinate phosphorus is involved is an open question* A tensiomstric study in brcmobenzene (12) showed formation of [(CH-^Pjg'FCl^ which was isolated as a white solid* Tertiary amines have not been ob­ served to form addition complexes with phosphorus pentachloride* Instead* dehydrogenation occurs with resultant formation of the amine hydrochloride (12*13)* Stable pyridine and dimethylfoxmamide com­ plexes of pheoyltetrafluorophosphorane* * have been
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