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Charlesbarlowphdthesis1967 Original C.Pdf University of St Andrews Full metadata for this thesis is available in St Andrews Research Repository at: http://research-repository.st-andrews.ac.uk/ This thesis is protected by original copyright i INVESTIGATION OF THE CHEMISTRY OF PHOSPHORUS FLUORIDES A Thesis presented for the degree of Doctor of Philosophy in the Faculty of Science of the University of St. Andrews by Charles George Barlow, B.Sc. United College of St. Salvator and September, 1967. St. Leonard, St. Andrews. ii I declare that this thesis is my own composition, that the work of which it is a record has been carried out by myself, and that it hss not been submitted in any previous application for a Higher Degree. The thesis describes results of research carried out at the Chemistry Department, United College of St. Salvator and St. Leonard, University of St. Andrews, under the supervision of Dr. J.F. Nixon since the 1st October 1964, the date of my admission as a research student. iii I hereby certify that Charles George Barlow, has spent eleven terms at research work under my supervision, has fulfilled the conditions of Ordinance No. 16 (St. Andrews) and is qualified to submit the accompanying thesis in application for the degree of Doctor of Philosophy. Director of Research. ACKNOWLEDGEMENTS I should like to thank Dr. J„F. Nixon for suggesting the topic of research and for his continued advice and encouragement during the period in which the work was carried out. In addition, I am indebted to Dr. K. Webster for his invaluable advice, Dr. T. Gilson and R.E. Hester for recording the Raman spectra end Dr. G.S. Ready for recording some of the nuclear magnetic resonance spectra. Thanks are also due to the Science Research Council for the award of a Research Studentship for the period during which the work was carried ouu. CONTENTS Page PART I, the co-ordination chemistry of fluorophosphines Introduction Metal Carbonyls 1 Fiuorophosphines 20 Discussion Results 31 Vibrational Spectra 40 Nuclear Magnetic Resonance Spectra 61 PART II, the reactions of difluorotrlchlororeethylphosphine Introduction Difluorotricnloromethylphosphine 74 DialkylaininocLi fluorophosphines 76 Diacussicn 81 EXPERIMENTAL SECTION 90 Purification of Starting Materials 92 Preparations 96 vx Page PART I Preparation of trans - (PI1' ) 108 ^Mo (CO) 0 " tran3-(CCl PF ) Mo(CO) 109 o ^ O O :t trans-:CF„PF ) Mo(CO) 110 o O *5 " trans-[(CF3)2FF]3Mo(CO)3 110 " trans-[{C F?) PF]gMo(CO)3 112 React I :>n between (CF ) P and C_H Mo(CO) 113 GO ' O O Preparation of ci3-(PFj)^Mo(C0)^ 114 " cis-(acl3PF2)2Mo(CO)4 115 " " c.i?-{CF-PF Kl.lo(CO). 117 3 X x 4 " cis-[(CF3)2PF]2Mo(CO)4 113 " c.i s - [ (CF_ ) _P ] „Mo (CO) . 119 c *> Z 4 " cls-(PF3)2Cr(CO)4 120 PART II Reaction between (C H ) NH and CC1„PF 121 Z O Z O z C_H. N and CC1„PF0 122 5 i.1 a2 C4H0N and CC13PF2 123 Preparation of 0.HoNPCl 124 4 o Z vii Page Fluorination of C H NPC1 126 4 b 2 Action of heat upon C.H NFP 128 4 3 2 Reaction between (OH ) PH and CC1 PF 129 o 2 o 2 (CF3)2PH + CC13PF2 132 CH_SH + 0C1„PF 133 3 o ? PF_ + CH.SH + (C HC)^N. 133 o *-» 2 o Reaction between (CH3)2NH and trans- (CCl3PF2)3Fto(CO)3 135 Reaction between C_H,,N and trans- 5 11 — (CCl3PF2>3Mo(CO)3 136 Reaction between C H _N and cis- 5 It (CC13PF2)2MO(CO)4 131 Reaction between HC1 and cis- (C H NPF ) Mo(CO) 138 5 10 23 3 Appendix Character tables for C , C groups s 2v Computer Programmes viii TABLES Fluorophosphines Following page 22 Metal (0) Trifluorophosphines and Carbonvltrif1uorophosphines 24 Raman Spectra of Three Fluorophosphine Kolybdenum Tetracarbonyls 44 Overtone and Combination Bands On Page 45 Force Constants for " trans-(L)- . - -MQ(CO)„ j J Complexes Following Page 43 Force Constants for cis-(L)rMo(CO) 2 (k. 2k ) 49 c Force Constants for cis-(L)^Mo(CO)^ (k 4 2k ) 49 t c 13. Calculated and Experimental C - 0 Frequencies for trans-(L)^Mo(CO) 52 13' Calculated ancl Experimental Frequencies for cis-(L) Mo(CO)^ 54 Force Constants of cis_~(L)_Mo(CO)_O Complexes of Phosphorus-Fluorine Ligands 58 Infrared Spectra of the Fluorophosphine Complexes 60 Changes in N.M.R. Parameters upon Complexation 73 ix N.M.R. Spectra, Part I Following Page 73 Infrared Spectra, Part II "" 89 N.M.R. Spectra, Part II >* " 89 DIAGRAMS 1. Bonding in phosphine-transition inetal complexes. Following Page 7 2. Structures of cvcloheptatriene molybdenum tricarbonyl and bicycloheptatriene molybdenum totracarbonyl. Following Page 31 3. Carbonyl stretching modes of (L) Mo(CO) o o and (L)y,Mo(C0)4 complexes. Following Page 39 4. Overtone and combination bands of three cis-(L) Mo(CO) complexes. On Page 45 5. Correlation diagrams of the assignments of carbonyl stretching frequencies. Following Page 45 6. Graph of n against k1 for (lO^MoCCO)^^. Following Page 56 7. Infrared Spectra of fluorophosphine complexes. Following Page 60 19 8. F N.M.R. Spectra showing non-equivalence of ligands in some (DgMo(CO)g complexes. Following Page 63 X 19 31 9, 10. F and P N.M.R. Spectra, experimental and calculated of cis-(PF^)JWo(C0)^ Following Page 66 19 11. F N.M.R. Spectrum, experimental and calculated of cis-(CCl_PF ) Mo(CO) ~ Following Page 67 k) AA 4 31 12. Experimental P N.M.R. Spectrum of cis- (CC13PF2)2Mo(C0)4 Following Page 67 13. Apparatus for the preparation of CF^I Following Page 99 PART I The Co-ordination Chemistry of Fluorophosphines, INTRODUCTION The first transition metal carbonyl to be isolated was nickel tetracarbonyl, in 18901, as the product in the corrosion of nickel by carbon monoxide, Carbonyls of some other transition metals have also been known for a long time. The direct reaction of carbon monoxide with the metal has produced the corresponding metal carbonyl only with nickel, iron, or cobalt. Other metal carbonyls have been synthesised by reduction of metal salts or complexes in 2 the presence of carbon monoxide, usually under high pressure . Transition metal carbonyls have been used as intermediates in 3 4 industrial syntheses such as the "Fischer-Tropsch" and "Oxo" processes, although their importance was not always recognised. 5 The us£ of metal carbonyls in organic syntheses has been reviewed . The metal carbonyls were remarkable in their properties, especially in view of the poor donor ability of carbon monoxide 0 towards boron compounds . The lack of any increase in electron density around the metal atom suggested that some mechanism other than just o*bonding between carbon and metal was involved. Electron 7 diffraction studies on nickel tetracarbonyl and the hexacarbonyls Q of Group VIB metals showed the metal-carbon bond lengths to be shorter than expected for a single bond. Pauling suggested that nickel carbonyl contained a partial double bond between nickel and 9 carbon which involved the metal 3d electrons • -2- Transition metal compounds have been prepared which contain both terminal and bridging carbonyl groups and metal-metal bonds have also been found in some of the compounds. The X-ray structure determination of iron enneacarbonyl, Fe^tCOjg, showed the presence of terminal and bridging carbonyl groups and an iron-iron bond1^. The binary metal carbonyls are usually diamagnetic; vanadium hexacarbonyl is one of the few exceptions, and their structures can be rationalised by the "inert gas rule". Terminal carbonyl groups are assumed to donate two electrons to the metal, bridging carbonyls one electron, and a metal-metal bond is assumed to contain one electron from each metal. Using these assumptions, the metal is usually found to attain the same configuration as the next inert gas. -3- In the years following 1950 Chatt published the results of 11 12 on studies the co-ordination chemistry of platinum ' . Some ligands were found to weaken the bond trans to them much more than bonds in the cis position. The ligands which caused the greatest "trans effect" combined weakly or not at all with electron acceptors such as BHg or AlClg, which had no occupied d orbitals. It was proposed that ligands which caused largo "trans effects", such as CO, PF_, or C-H. formed strong bonds with metals having electrons «7 / " in their outer d shell because of the formation of a 71 bond which used the metal d electrons in addition to the normalcfbond between carbon and metal. A similar type of bonding had been postulated 13 by Pauling to explain the properties of some of these ligands Theoretical calculations have shown that the existence of 14 p_ - d . and d - d bonding is energetically possible . Tv 11 il Tlr V -4- The bonding molecular orbitals of carbon monoxide may be 2*2 4 2 represented as(cr)(ir)(7t )(c5"), indicating one <yand s s x,y t two Tl bonds between carbon and oxygen. A lone pair of electrons is left on both carbon and oxygen. The molecular orbital of lowest energy after is the ^ antibonding orbital, which is unoccupied in carbon monoxide. The dativeefbond from carbon monoxide to a transition metal is formed by donation of the unshared pair of electrons on the carbon into an empty orbital on the metal. The increase in electron density which this process places on the metal could be diminished by donation of electrons from an occupied metal d^ or dp^. hybrid orbital into the empty % orbital of carbon monoxide.
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