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Borane-Containing Ligands Based on Thioxanthene, Xanthene and Acridine

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PLATINUM COMPLEXES OF NEW BORANE-CONTAINING LIGANDS BORANE-CONTAINING LIGANDS BASED ON TillOXANTHENE, XANTHENE AND ACRIDINE: SYNTHESES AND PLATINUM COORDINATION CHEMISTRY By NATALIE L. BLACKWELL, B. Sc. A Thesis Submitted to the School ofGraduate Studies in Partial Fulfillment ofthe Requirements for the Degree Master ofScience McMaster University © Copyright by Natalie L. Blackwell, September 2006 Master ofScience (2006) McMaster University (Chemistry) Hamilton, Ontario TITLE: Borane-Containing Ligands Based on Thioxanthene, Xanthene and Acridine: Syntheses and Platinum Coordination Chemistry AUTHOR: Natalie L. Blackwell, B. Sc. (Windsor University) SUPERVISOR: Dr D. J. H. Emslie NUMBER OR PAGES: xviii, 137, XX ii Abstract Ligand backbones based on xanthene, thioxanthene and acridine (XPB, TXPB and APB) have been targeted as scaffolds for the formation of rare compounds containing Lewis basic phosphine and Lewis acidic borane moieties. The resulting complexes with Pt(O) and Pt(II) reagents are expected to possess diverse reactivity compared to traditional platinum phosphine adducts owing to the strategically appended borane Lewis acid. tau tBu tau tau Two ligands, 2,7-di-(tert-butyl)-4-diphenylboryl-5-diphenylphosphino-9,9­ dimethylthioxanthene (TXPB) and 2,7-di-(tert-butyl)-4-diphenylboryl-5­ diphenylphosphino-9,9-dimethylxanthene (XPB), have been synthesized and reacted with the platinum reagents [PtCh(COD)], [PtMe2(COD)] and [Pt(nbe)J]. In the case ofTXPB, two new Pt(II) compounds [PtCl(~-Cl)(TXPB)] and [PtMePh(TXPBPh,Me)] have been formed, isolated and characterized. In both compounds, X-Ray analysis shows that the S 111 and the P atoms bind to the Pt center drawing the metal into the vicinity of the B group. In [PtCl(J.t-Cl)(TXPB)], a chloride is seen to bridge between the Pt and B, whereas [PtMePh(TXPBPb,M')] shows that a methyl groups has been transferred to the boron with concomitant transfer of a phenyl group to Pt. Reaction with the platinum(O) precursor [Pt(nbe)3] led to formation of an unstable complex, tentatively assigned as [Pt(nbe)TXPB]. Analogous studies with the new xanthene-derived ligand, XPB, led to starkly different results. In the reaction with [PtCh(COD)], an insoluble product, perhaps a dinuclear complex with bridging chlorides, was formed. No reaction occurred with [PtMe2(COD)], presumably because of non-participation of the 0 ligand. However, with [Pt(nbe)3], a stable complex, [Pt(nbe)VQ>B], was observed. Synthesis of a third ligand scaffold APB has been initiated where the pyridine moiety is expected to allow strong chelation of Pt as observed with TXPB. An advanced intermediate AFBr has been synthesised where the backbone has been created through a ring closure reaction positioning two different halides as required for sequential addition ofthe phosphine and borane groups ofthe target compound. lV Acknowledgements I would like to thank my supervisor Dr. D. Emslie for allowing me to carry out this research project under his supervision and for all ofhis help and guidance. I am grateful to the other members of the group, especially Carlos Cruz for his companionship and sharing oflab space and glassware. I would like to extend my gratitude to Drs. I. Vargas-Baca and P. Harrison for their help and effort put into being on my committee. I would also like to thank Drs. Jim Britten and Laura Harrington for X-ray structure determination. I finally wish to extend my gratitude to my family for their support and perseverance, and especially to my husband James. v Table ofContents Descriptive Note ii Abstract 111 Acknowledgments v Table ofcontents V1 List ofFigures xi List ofSchemes xiv List ofTables XV List ofAbbreviations and Symbols XVI V1 Chapter 1: Introduction 1 1.1 Lewis Acids and Lewis Bases 1 1.1.1 Group 13 Lewis Acids 2 1.1.2 Transition Metal Lewis Acids 3 1.1.3 Group 15 Lewis Bases 4 1 1.2 Conventional T) - Bonding Interactions Between Transition Metals 5 and Ligands 1.2.1 Ligand To Metal Sigma and Pi Donation 5 1.2.2 Metal To Ligand Pi Donation 6 1.3 Transition Metals as Sigma Donors 9 1.3.1 Transition Metal-Borane Complexes 10 1.3.2 Transition Metal- Group 13 Lewis Acid (AlR3, GaR3, 14 and lnR3) Complexes 1.3.3 M-ER3(E =B, Al, Ga, In) Complex Ambiguity 15 1.3.4 Boryl Metallocenes: Weak TM-BR3 Interactions 18 1.4 Other Hybrid Lewis Acid/Base Compounds 20 1.4.1 Molecules Designed for Bifunctional Activation and Catalysis 20 1.4.2 Bifunctional Molecules Designed for Other Applications 22 1.5 A Brief Overview ofSome Boron Lewis Acid Chemistry 23 1.5.1 11Boron NMR Spectroscopy 26 1.6 A BriefOverview ofOrganoplatinum Chemistry 27 vii Chapter2: Ligand Design and the Platinum Chemistry ofPhosphine/ 31 Thioether/ Borane Ligand, TXPB 2.1 Design ofHybrid P,B-Based Ligands 31 2.1.1 Platinum Complexes from a Thioxanthene-based Ligand TXPB 36 2.1.2 Synthesis ofa Phosphine/Thioether!Borane ligand (TXPB) 37 2.1.3 Reaction ofTXPB with [PtCh(COD)] 38 2.1.4 Introduction to Cyclic V oltammetry 44 2.1.5 CV of [PtCl(JJ.-Cl)(TXPB)] vs. [PtCh(TXPH) 45 2.1.6 Reaction ofTXPB with [PtMe2(COD)] 49 2.1.7 Reaction ofTXPB with [Pt(nbe)3] 64 2.1.8 Reaction ofTXPB with [Pt2(dba)3] 70 2.2 Summary ofTXPB Coordination Chemistry 72 viii Chapter 3: Synthesis and the Platinum Chemistry of Phosphine 73 /Ether/Borane Ligand, XPB 3.1 Applications ofthe Versatile Xanthene Backbone 73 3.1.1 Expected Coordination Behaviour for Xanthene-Based Hybrid 77 Phosphine/Borane Ligands 3.1.2 Synthesis of9,9- dimethyl-5-diphenylborano-4- 80 diphenylphosphino -2,7 -di(tert-butyl)xanthene (XPB) 3.1.3 Metal Complexation with the XPB ligand 86 3.1.4 Reaction ofXPB with [PtCh(COD)] 87 3.1.5 Reaction ofXPB with [PtMe2(COD)] 91 3.1.6 Reaction ofXPB with [Pt2(nbe)3] 92 3.2 Summary ofXPB Coordination Chemistry 96 ix Chapter4: Towards Extremely Rigid Phosphine/Acridine/Borane Ligands 98 4.1 Acridines 98 4.1.1 Established Synthetic Methods To Acridine Derivatives 101 4.2 Phosphine/Borane Ligands Based on Acridine 104 4.2.1 Attempted Synthesis of4-diphenylboryl-5-diphenylphosphino- 104 acridine (APB) 4.2.2 Design ofa New Phosphine/Acridine/Borane Ligand 109 4.2.3 Synthesis ofthe Intermediate 4-fluoro-3-iodotoluene 110 4.2.4 Synthesis ofthe Intermediate (6-bromo-2-carbox.y-4- 111 methylphenyl) -(2-fluoro-4-methylphenyl)amine 4.2.5 Synthesis ofthe Intermediate 4-bromo-9-chloro-5-fluoro-2,7- 112 dimethylacridine 4.2.6 Synthesis ofthe Intermediate 4-bromo-5-fluoro-2,7- 114 dimethylacridine 4.2.7 Attempted Synthesis ofIntermediate 4-diphenylphosphinyl-5- 117 fluoro-2, 7 -dimethylacridine 4.3 Conclusions on Acridine Work 119 Chapter 5: Experimental 120 References 131 Appendix X-ray Crystallographic data I X List of Figures 1.1 Examples ofa Lewis Acid and a Lewis Base 1 1.2 An Activated Adduct 3 1.3 Sigma and Pi Donation From Ligand to Metal 6 1.4 Dewar-Chatt-Duncanson Bonding Diagram for Alk.yne Ligands 7 1.5 Pi Backbonding Leading to Oxidation State Change 8 1.6 Classic Text-Book Example ofa Transition Metal Borane Complex 10 1.7 Recent Examples ofMetal Borane Complexes 11 1.8 PBP Ligand and PBP-Rh Complexes 14 1.9 Examples Highlighting Ambiguities in TM-ER3 Complexes 16 1.10 Bridging Boryl Complexes Involving M---+B Interactions 17 1.11 Isolectronic Ferrocenyl Carbocations and Boranes 19 1.12 Literature Examples ofBifunctional Ligands Containing Both Lewis 21 Acidic and Lewis Basic Groups 1.13 Example ofIntramolecular LAILB Adduct Formation 22 1.14 Strategies to A void Internal Complexation 23 1.15 Some Examples ofAryl Boranes 25 1.16 Examples ofPt(O) Complexes 28 2.1 Examples ofChelating Ligands Based on Aromatic Backbones 32 2.2 Target Borane-Containing Ligands 34 2.3 31P NMR Spectrum of1 39 2.4 X-ray Structure of[Pt(X)(f.J.-Cl)(TXPB)], [X= Cl (80%), Br (20 %)] 40 xi 2.5 The TXPH Ligand 45 2.6 Cyclic Voltammograms for [PtCh(TXPB)] and [PtCh(TXPH)] at 46 200mV/s 2.7 Zwitterionic [PtMe(TXPB-Me)] 50 2.8 31P NMR Spectrwn of2 51 2.9 X-Ray Structure of2 with 50% Probability Ellipsoids, H-atoms Omitted 52 for Clarity 2.10 Expanded Alkyl Section of1H NMR Spectrwn of2 56 2.11 VT 1H NMR Spectra of2, with Enlarged Alkyl Region at -80° C 57 2.12 Potential Structure of [Pt(nbe)(TXPB)] 64 2.13 1H NMR Spectra of(a) [Pt(nbe)(TXPB)] and Starting Materials 66 (b) [Pt(nbe)3] and (c) Free nbe 2.14 31P NMR Spectrwn of[Pt(nbe)(TXPB)] 67 2.15 31P NMR Spectrwn ofDecomposed [Pt(nbe)TXPB)] 67 2.16 31 p NMR Spectrwn of[Pt(nbe)(TXPB)] + PPh3 68 2.17 31P NMR Spectrwn of [Pt(nbe)(TXPB)] + PtBu3 69 2.18 Resonance Forms of [Pd(dba)TXPB] 71 3.1 Xanthene 73 3.2 Examples ofUseful Compounds Based on the Xanthene Skeleton 74 3.3 Xantphos 75 3.4 Bidentate Ligands Based on Xanthene Backbone 76 3.5 Examples of0-M Coordination in a Xantphos Complex 78 Xll 3.6 Comparison ofMetal Coordination Possibilities Due to Lewis 79 Basic Groups on TXPB, XP2 and XPB Backbones 3.7 1H NMR Spectrum ofXPBr, with 31P NMR Spectrum in Inset 83 3.8 1H NMR Spectrum of3, with 31 P NMR Spectrum in Inset 85 3.9 X-ray Crystal Structure of3, at 50% Probability Level Ellipsoids 85 (Hydrogen Atoms Omitted for Clarity) 3.10 1H NMR and 31P NMR Spectra ofXPB and [PtCh(COD)] Reaction 88 3.11 Possible Monomeric Products/Intermediates from XPB and 89 [PtCh(COD)] 3.12 Possible Bis-Phosphine Complex and Dimer Formed From XPB with 90 [PtCh(COD)] 3.13 1H NMR Spectrum of [Pt(nbe)(XPB)], with 31P NMR Spectrum in Inset 93 3.14 [Pt(nbe)2(XPB)] 94 3.15 Oxidative Addition at [Pt(nbe)2(XPB)] and [Pt(nbe)2(XPH)] 95 4.1 Acridine 98 4.2 Examples ofUseful Acridine-based Compounds 98 4.3 Structure ofAcriphos and Analogues 99 4.4 Examples ofAcriphos
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    _________________________________________________________________________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.
  • Selective Additions to Unsaturated Carbon-Carbon Bonds by the Use

    Selective Additions to Unsaturated Carbon-Carbon Bonds by the Use

    Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2014 Selective Additions to Unsaturated Carbon- Carbon Bonds by the Use of N-Heterocyclic Carbene-Copper(I) Catalysts Brian A. Ondrusek Follow this and additional works at the FSU Digital Library. For more information, please contact [email protected] FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES SELECTIVE ADDITIONS TO UNSATURATED CARBON-CARBON BONDS BY THE USE OF N-HETEROCYCLIC CARBENE-COPPER(I) CATALYSTS By BRIAN A. ONDRUSEK A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy Degree Awarded: Summer Semester, 2014 Brian Ondrusek defended this dissertation on July 1st, 2014. The members of his supervisory committee were: D. Tyler McQuade Professor Directing Dissertation Bruce Locke University Representative Michael Roper Committee Member Gregory Dudley Committee Member Igor Alabugin Committee member The Graduate School has verified and approved the above-named committee members, and certifies that the dissertation has been approved in accordance with university requirements. ii I dedicate this effort to my family, without whose support I could never have accomplished all that I have. iii ACKNOWLEDGMENTS I would like to acknowledge Dr. Tyler McQuade for taking a very green graduate student and whipping me into shape. I’m sure that at times it was no easier for him than it was for myself, but his constant support has enabled me to develop as I have into a more mature scientist. He was always willing to help me understand concepts with which I was struggling, and he was always willing to allow me to explore topics in which I was interested.