_________________________________________________________________________Swansea University E-Theses The synthesis and characterisation of some novel compounds containing Pt-Se bonds. Webster, Christopher Alan How to cite: _________________________________________________________________________ Webster, Christopher Alan (2006) The synthesis and characterisation of some novel compounds containing Pt-Se bonds.. thesis, Swansea University. http://cronfa.swan.ac.uk/Record/cronfa43110 Use policy: _________________________________________________________________________ This item is brought to you by Swansea University. Any person downloading material is agreeing to abide by the terms of the repository licence: copies of full text items may be used or reproduced in any format or medium, without prior permission for personal research or study, educational or non-commercial purposes only. The copyright for any work remains with the original author unless otherwise specified. The full-text must not be sold in any format or medium without the formal permission of the copyright holder. Permission for multiple reproductions should be obtained from the original author. Authors are personally responsible for adhering to copyright and publisher restrictions when uploading content to the repository. Please link to the metadata record in the Swansea University repository, Cronfa (link given in the citation reference above.) http://www.swansea.ac.uk/library/researchsupport/ris-support/ The Synthesis and Characterisation of Some Novel Compounds Containing Pt-Se Bonds Christopher Alan Webster Department of Chemistry University of Wales Swansea November 2006 ProQuest Number: 10821502 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10821502 Published by ProQuest LLC(2018). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 LIBRARY Acknowledgements Firstly I would like to thank Dr. Chris Morley, my supervisor for his invaluable support, guidance and encouragement. My thanks also go to Prof. Massimo Di Vaira for all his support during my stay at the University of Florence and for the crystal structure determinations he carried out. Thanks to Su Jing, the other half of Swansea’s Inorganic/Organometallic Research Group, for doing such a phenomenal amount of work that I had to work hard just to keep up! Thanks to the players of chemistry rugby past and present - Lee, Paul, Des, Dave, Hans, Big Chris, Bleddyn, Fergus, Matt B, Dave (undergrad), Geraint, Will, John T and Brendan - for making Friday lunchtimes something to look forward to. Thanks to Ian Matthews and Dr. Suzy Kean for running NMR spectra, John Tregembo for glass blowing and Stan Szajda for finding equipment and chemicals whenever I needed them. Thanks to the EPSRC Mass Spectrometry Service Centre for all of the mass spectral data. Thanks to Johnson Matthey pic for the loan of platinum and palladium salts. Contents Abstract i Abbreviations iii Chapter 1: Introduction 1 1.1 Introduction 1 1.2 Platinum, Sulphur and Selenium 2 1.3 Organoselenium Coordination Chemistry 4 1.4 Complexes with Selenoether Ligands 5 1.4.1 Complexes Containing Monodentate Selenoether Ligands 5 1.4.2 Complexes Containing Bidentate Selenoether Ligands 6 1.4.3 Complexes Containing Polydentate Selenoether Ligands 9 1.4.4 Complexes of Unsaturated Diselenoethers 12 1.5 Phosphines as Ligands in Transition Metal Complexes 13 1.5.1 Synthesis 13 1.5.2 The Metal-Phosphine Bond 13 1.5.3 Steric Factors 14 1.5.4 NMR 15 1.5.5 Metal Phosphine Complexes in Catalysis 16 1.6 Complexes of 1,2,3-Selenadiazoles and 1,2,3-Thiadiazoles 19 1.6.1 The Synthesis of 1,2,3-Selena- and 1,2,3-Thiadiazoles 19 1.6.2 Complexes Containing 1,2,3-Selena- and 1,2,3-Thiadiazole Ligands 19 1.6.3 Reactions of 1,2,3-Selena- and 1,2,3-Thiadiazoles 21 1.7 Synthesis and Reactions of 1,4-Diselenins 27 1.8 Synthesis and Reactions of 1,2-Diselenins and Other Compounds with an 30 Se-Se Bond 1.9 Diselenolenes 34 1.10 Transition Metal Dithiolenes 42 1.10.1 Dithiolenes Containing the dmit Ligand 42 1.10.2 Ferromagnetic and Antiferromagnetic Dithiolenes 44 1.10.3 Dithiolenes as Q-Switch Dyes in Near-IR Lasers 45 1.11 The Reactions of Selenophenes with Transition Metal Complexes 47 Chapter 2; The Syntheses, Reactions and Characterisation of 54 Some Platinum Diselenolenes 2.1 The Synthesis and Reactions of [Pt(Se2C8Hi 2 )(PPh3 )2 ] 54 2.1.1 The Synthesis of [Pt(Se2C8Hi 2 )(PPh3 )2 ] 54 2.1.2 Reactions of [Pt(Se 2 C8 H]2 )(PPh3 )2 ] with Trialkylphosphines and Phosphites 56 2.1.3 Reactions of [Pt(Se 2 C8 Hi2 )(PPh3 )2 ] with Chelating Phosphines 59 2.1.4 Attempted Syntheses of [Pt(Se2C7Hio)(PPh 3 )2 ] and [Pt(Se2 C6 H8 )(PPh3 )2 ] 67 2.2 The Synthesis of Platinum Diselenolenes [Pt(Se2Cn+ 4 H 2 n+4 )(PR3 )2 ] 69 2.3 Attempted Syntheses of [PtSe4(PR3)2] 84 Chapter 3: The Reactions of Cycloalkeno-l,2,3-thiadiazoles and 86 Cycloalkeno-l,2,3-selenadiazoles with Platinum (0) Phosphine Complexes 3.1 Reactions of [Pt(C 2 H4)(PR3)2 ] with Cycloalkeno-1,2,3-thiadiazoles 86 3.2 Reactions of [Pt(C2H 4 )(PR3)2 ]/[PtCl2(PR3 )2 ] with Cycloalkeno-1,2,3- 99 selenadiazoles 3.3 The Reaction of [Pt(PPh3) 4 ] with Cyclohexeno-1,2,3-selenadiazole 108 3.4 Reactions of [Pt(C 2 H4)(PR3)2] with Cycloalkeno-1,2,3-selenadiazoles 111 3.5 Reactions of [Pt(SeCn+ 4 H2n+4 )(PR3 )2 ] with Mel 117 3.6 Reactions of [PtI{Se(Me)Cn+ 4 H2n+4 }(PR3 )2 ] with T1PF6 124 Chapter 4; The Syntheses, Reactions and Characterisation of Some 130 Complexes Derived From Selenophene 4.1 The Reactions of [Pt(C2H4)(PR3)2] with Selenophene 130 4.2 Reactions of [Pt(SeC 4 H4)(PBu3)2] 138 4.3 Miscellaneous Reactions 140 4.3.1 Reactions of [Pt(C 2 H4 )(PR3)2 ] with Thiophene and 2,5-Diphenyltellurophene 140 4.3.2 Reactions of Palladium(O) Phosphine Complexes with Selenophene 141 Chapter 5: The Reactions of Compounds Containing an Se-Se Bond 142 with Zerovalent Platinum and Palladium Trialkvlphosphine Complexes 5.1 The Reactions of (PhSe)2 and (FcSe)2 with [Pt(C2H4)(PR3)2] and with 142 [Pd2(dba)3].dba/PR3 5.2 The Reactions of (PhTe)2 and (FcTe)2 with [Pt(C2H4)(PR3)2] and with 152 [Pd2(dba)3] .dba/PR3 5.3 The Reactions of (FcSe)2 and (FcTe)2 with [Pt(PPh3)4] 155 5.4 The Reactions of 6w-Benzo-l,2-diselenin with [Pt(C2H4)(PR3)2] and 156 with [Pd2(dba)3].dba/PR3 5.4.1 The Syntheses of [Pt(Se 2 Ci2 H8 )(PR3 )2 ] and [Pd(Se2 Ci2 H8 )(PR3 )2 ] 156 5.4.2 The Syntheses of [Pd 2 (Se2 C 12 H8 )2 (PR3 )2 ] 169 Chapter 6: An X-ray Crystallographic Study of Some Organometallic 178 and Coordination Compounds 6.1 X-ray Crystallography 178 6.2 Crystal Structure Determinations 182 6.3 Crystal Structure Determinations of fr<ms-[Pt(SePh)2(PR3)2] (R = Et, Bu), 183 ^<ms-[Pt(SeFc)2(PBu3)2] and [Pt(Se2Ci2H8)(PEt3)2] 6.3.1 Crystal Structure Determinations of /nms-[Pt(SePh) 2 (PBu3 )2 ] and 183 frW2S-[Pt(SeFc)2(PBU3)2] 6.3.2 Crystal Structure Determination of [Pt(Se 2 Ci2 H8 )(PEt3 )2 ] 189 6.3.3 Crystal Structure Determination of drafts-[Pt(SePh) 2 (PEt3 )2 ] 193 6.4 Crystal Structure Determination of [Pd2(Se2Ci2Hg)2(PEt3)2] and Partial 198 Crystal Structure Determination of /ra«s-[Pd(SeFc)2(PBu3)2] 6.4.1 Crystal Structure Determination of [Pd 2 (Se2 Ci2 H8 )2 (PEt3 )2 ] 198 6.4.2 Partial Crystal Structure Determination of /r<ms-[Pd(SeFc) 2 (PBu3 )2 ] 203 6.5 Crystal Structure Determination of 206 [Pt { SC(R')=C(R2)N=NC(R i )=C(R2)S} (PEt3)] 6.6 Crystal Structure Determination of 213 [PtCl{FcSe(CH2)3Se(CH2)3 SeFc}][PF6] 6.7 Crystal Structure Determinations of FcSe(CH2) 3 SeFc and 217 [M { FcE(CH2)3EFc } (CO)4] 6.7.1 Crystal Structure Determination of FcSe(CH 2 )3 SeFc 217 6.7.2 Crystal Structure Determinations of [M{FcE(CH 2 )3 EFc}(CO)4] 220 6.8 Crystal Structure Determination of frawj^PdCl^T^-FcSeCKkSeFcJJ 229 6.9 Partial Crystal Structure Determination of [PdCl2{FcSe(CH2)2SeFc}] 233 Chapter 7: Experimental Details 235 7.1 Experimental Details 235 7.2 Synthetic Procedures 237 References 244 Abstract The main aim of the work described in this thesis was to investigate the potential of reactions of Pt(0) phosphine complexes with selected organoselenium reagents to provide routes to diselenolenes and related compounds with Pt-Se bonds. Chapter 1 reviews the background to this work, and introduces some relevant classes of compound. Surveys of the coordination chemistry of organoselenium ligands such as selenoethers, 1,2,3-selenadiazoles, 1,4-diselenins and selenophenes are included. The properties of dithiolenes and diselenolenes are also discussed. Each of Chapters 2-5 deals with a specific type of reaction, and the characterisation of the products, in particular by multinuclear NMR spectroscopy, X-ray diffraction and mass spectrometry, supplemented by other techniques as appropriate.