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Some Reactions of Phosphorusfluorine Compounds with Platinum Metal Hydride Complexes Philip G. Page Ii Thesis Presented For

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Some Reactions of Phosphorusfluorine Compounds with Platinum Metal Hydride Complexes Philip G. Page Ii Thesis Presented For ii Some Reactions of Phosphorusfluorine Compounds with Platinum Metal Hydride Complexes Philip G. Page Thesis presented for the degree of Doctor of Philosophy University of Edinburgh Seotember 1983 To my parents Declaration This thesis has not been submitted, in whole, or in part, previously for any degree at any university. All the work is original, under the supervision of Professor E.A.V. Ebsworth; where this is not the case, credit has been duly given. () Table of Contents Acknowledgements Abstract Chapter 1 Introduction References Chapter 2 Experimental Techniques and Instruments N.m.r. Experiments Chemical Reagents Volatile Reagents Metal Complexes Used C. Solvents Used References Chapter 3 Some Reactions of H 2Pt(PCy 3 ) 2 and HPtC1(PCy3) 2 Introduction Some reactions of H 2Pt(?Cy 3 ) 2 2.1 with EX (X = Cl, Br, I) 2.1.1 Earlier work 2.1.2 New work 2.1.3 The spectra and discussion 2.2 with H 2 E (E = 5, Se) 2.2.1 Earlier work 2.2.2 New work and spectra - 2.2.3 Discussion 2.3 with HPF 2E CE = 0, 5, Se) 2.3.1 Preliminary and earlier work 2.3.2 New work 2.3.3 Discussion. (i ) 2.4 with SiH 4 2.4.1 Earlier work 2.4.2 New work 2.4.3 Discussion 2.5 with PF 2 X (X = Cl, Br, I) 2.5.1 Earlier work 2.5.2 New work 2.5.3 Discussion 2.6 with HPF 2 Some of the reactions of HPt(PCy 3 ) 2 X (X = SiH 3 , S1H, SeH, PF 2O, PF 2 S, PF 2 Se) 3.1 Preliminary 3.2 The reactions of HPt(PCy 3 ) 2SiH 3 3.2.1 with HPF 2E (E = 0, S, Se) 3.2.2 with HC1, HBr, HI 3.2.3 with H 2 S and H 2 Se 3.3 The reactionsof HPt(PCy 3 ). 2EH (E = S, Se) 3.3.1 with HPF 2Y (E = S, Se; Y = S, Se) 3.3.2 with H 2 Y (E = S, Se; Y = 5, Se) 3.3.3 with SiH 4 (E = 5, Se) 3.4 The reactions of HPt(PCy 3 ) 2PF 2E (E= S, Se) 3.4.1 with SiH 4 , H 2 S and H 2 Se (E = S, Se) 3.4.2 with HX (E = S, Se; X = Cl, Br, I) Some conclusions on the reactions of H 2 Pt(PCy 3 ) 2 and its derivatives Some of the reactions of HPt(PCy 3 ) 2C1 5.1 Introductory 5.2 The reaction of HPt(PCy 3 ) 2 C1 with HPF 2 S 5.3 The reaction of HPt(PCy 3 ) 2Cl with (SiH3) 2 5.4 The reaction of HPt(PCy 3 ) 2 C1 with H 2PSiMe 3 5.4.1 The N.m.r. spectra 5.4.2 Discussion (in) Some of the reactions of HPt(PCy 3 ) 2 PH 2 6.1.. with B H 6 2 6.2 with HPt(PCy 3 ) 2 C1 6.3 with HPt(PEt 3 ) 2 C1 6.4 with AgI.PEt 3 The X-ray crystallographic structure of HPt (PCy 3 ) 2 PF 2 S 7.1 Description 7.2 Discussion References Chapter 4 Some reactions of HIr(CO) (PPh 3 ) 3 Introduction The reactions of HIr(CO) (PPh 3 ) 3 with HX (X = Cl, Br, I) The reactions of HIr(CO) (PPh 3 ) 3 with H 2 E (E=S, Se) 3.1 with H 2 S 3.2 with H 2 Se The reactions of HIr(CO) (PPh 3 ) 3 with HPF 2E (E = 0, S, Se) 4.1 The new work 4.2 The 31 P n.m.r. spectra 4.3 The 19 F n.m.r. spectra 4.3.1 The reaction of HIr(C0) (PPh 3 ) 3 with HPF 2O 4.3.2 The reaction of HIr(CO)(PPh 3 ) 3 with HPF 2 S 4.3.3 The reaction of HIr(C0) (PPh 3 ) 3 with HPF 2 Se 4.4 The 'H n.m.r. spectra 4.4.1 Previous related work 4.4.2 The - H n.m.r. spectra of HIr(C0)- (PPh 3 ) 3 + HPF 2E (E = 0, 5, Se) 4.5 The 77 Se spectrum of PF 2 Se 4.6 Discussion (iv) The reaction of HIr(CO) (PPh 3 ) 3 with PF 3 5.1 The 31 P n.m.r. spectra 5.2 The 19 F n.m.r. spectra 5.3 The 'H n.m.r. spectrum 5.4 Discussion The reactions of HIr(CO) (PPh 3 ) 3 with PF 2X (X = Cl, Br, I) 6.1 The 31 P n.m.r. spectra 6.2 The 19 F n.m.r. spectra 6.3 The 'H n.m.r. spectra 6.4 Discussion The reactiorof HIr(CO) (PPh 3 ) 3 with (PF 2 ) 2E (E = 0, S, Se) 7.1 with (PF 2 ) 2 0 7.2 with (PF2 ) 2 S 7.3 with (PF 2 ) 2 Se 7.4 Discussion The reactions of HIr(C0) (PPh 3 ) 3 with HSiX 3 (X = F, Cl) 8.1 with HSiC1 3 8.2 with HSiF 3 8.3 Discussion The reaction of HIr(C0) (PPh 3 ) 3 with PF 2 CN and PF 2NCE (E = 0, S,.Se) 9.1 The reactions 9.2 The reaction of HIr(C0) (PPh 3 ) 3 with PF 2NCSe Some conclusions on the reactions of HIr(C0) (PPh 3 ) 3 Re.jrences (v) Chapter 5 Some reactionsof HRh(CO) (PPh 3 ) 3 Introductory The reactions in general The reaction5 of HRh(CO) (PPh 3 ) 3 with fluorinated phosphorus compounds 2.1 with HPF 2 E (E = 0, S 1 Se) 2.2 with PF 2X (X = Cl, Br, I) 2.2.1 with PF 2 I 2.2.2 with PF 2 G 2.2.3 with PF 2 r- 2.3 Some conclusions The reactions of HRh(CO) (PPh 3 ) 3 with MH 3X (M = Si, Ge; X = H,F,C1,Br,I,CH 31 SiH 3 ) 3.1 The reactions of HRh(C0) (PPh 3 ) 3 with GeH 3X (X = H,F,Cl,Br,I) 3.1.1 with GeH 4 3.1.2 with GeH 3F 3.1.3 with GeH 3C1 3.1.4 with GeH 3Br 3.1.5 The reaction of HRh(C0) (PPh 3 ) 3 with GeH 3 I 3.2 Some conclusions of the reactions of FIRh(CO)(PPh 3 ) 3 with germyl compounds 3.3 The reactions of HRh(C0) (PPh 3 ) 3 with silyl compounds 3.3.1 with SiH 4 3.3.2 with SiH 3C1 3.3.3 with Si 2 H 6 3.3.4 with CH 3 SiH 3 3.4 The reaction of HRh(C0) (PPh 3 ) 3 with H 2 Se Conclusions References Postgraduate Courses Attended (vi) Acknowledgements This thesis is the product of many people's work; without them, it would not exist. First, and foremost, my thanks go to Professor E.A.V. Ebsworth, whose guidance, stimulation and perseverance is an essential part of the thesis. Thanks are also due to Dr. D.W.H. Rankin, Dr. S. Cradock and Dr. J.D. Whitelock, whose experience with some of these systems and whose inspirations often saved the day. My sincere thanks are due to Mr. S.D.G. Henderson for his, help in the arts of glassblowing, both in teaching minor operations and in rectifying more serious problems, and in the general aspects of vacuum line and heavy metal chemistry; also, in part, thanks for the inspirations obtained during the solution of more difficult n.m.r. spectra. I include all the members of the inorganic research group for the many and various constructive suggestions. In the field of n.m.r., thanks are due to Mr. J.RA. Miller, for running the continuous wave n.m.r. spectra and teaching me the use of the Jeol FX60Q n.m.r. spectrometer; to Mr. L.E. Bell and Dr. A.S.F. Boyd for obtaining XL100 spectra and to Dr. D. Reed Mr. L.E. Bell, Dr. I.H. Sadler and Professor E.A.V. Ebsworth for obtaining spectra from the WH300 high field spectrometer; I also thank Professor E.A.V. Ebsworth for the guidance in solving the hardest spectra,. = co due b M. D. WOLI Kir,5110AI 40r tiq crtjslul sFucts (vii) The thesis would not be in easily readable form without the many hours put in by the typists, both in Edinburgh and at Dounreay, but particular thanks are due to Miss A. Erskine, Mrs M. Manson, Mr. D.H. Bruce and Mrs E. Spearing. I also thank the Science and Engineering Research Council for a maintainance grant, and the University of Edinburgh for a Hope prize scholarship award and laboratory facilities. (vUi) 7ncmr'm Nuclear magnetic resonance studies of platinum, iridium and rhodium phosphine hydride complexes are described, along with some of their reactions with fluorinated phosphines and small simple silyl and germyl molecules. Chapter 1 gives an introductory preface to the work described in the thesis and Chapter 2 describes the experimental details involved. Chapter 3 describes the oxidative addition and subsequent reductive elimination reactions of H 2Pt(PCyHex 3 ) 2 towards SiH 4 , H 2S, H 2 Se, HPF 2E (E = 0, S, Se) and HX (X = Cl, Br, I). In all of these cases, a transient trihydride platinum(IV) species was detected, although all of these intermediates evolved hydrogen gas at room temperature, to yield isolable solids.
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