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Aspects of the Transition-Metal Coordination Chemistry of Phenylphosphine by Simon Doherty A thesis submitted to the University of London for the degree of Doctor of Philosophy Department of Chemistry University College London 20 Gordon Street London WC1H-OAJ December 1990 ProQuest Number: 10797762 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 10797762 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 Abstract This thesis describes the synthesis and reactions of phosphido complexes of both the early and late transition-metals. The thermal reaction of dodecacarbonyltriruthenium with phenylphosphine (and its cyclohexyl analogue) was investigated and new trinuclear clusters with combinations of terminal phosphine, bridging phosphido and p^-phosphinidene ligands were isolated. These have been characterised by n.m.r. methods and the single-crystal structures of [Ru3(p-H) 2(p 3-PPh)(PPhH 2)(CO)8] and [Ru 3(p-H)(p-PPhH^CO)7] have been deduced. The pyrolysis of (Ru 3(|i3-PPh) 2(CO)9] was investigated and was found to yield new hexanuclear clusters of which the fluxional trigonal prismatic structures [R u^p-H )^- PPh) 2(p 4-PPh) 2(CO)12] and [Ru^fvPPhMPrPPh^CCO^J have been crystallographically determined. Their metal frameworks were found to have interesting features and are compared with the known structure [Ru 6(p 3-PPh) 2(p 4-PPh) 3(CO)12]. We have synthesised the terminal phosphine complexes [IrCl2(PMe2Ph) 3(PHR1R2)][C104] (R' = RJ = H, R‘ = H R 2 = Ph, R 1 = R2 = Ph) and these were found to deprotonate readily in the presence of base to afford the corresponding neutral phosphido complexes. Reactions of these phosphido complexes with both organic and metallic electrophiles was investigated and the crystal structure of [{IrCl2(PMe2Ph) 3(PH2))2Au][C104] was determined. Investigating the origin of the broad n.m.r. spectrum of [IrCl^PMe^hOJ [CIOJ (formed from the reaction of the phosphido complex [IrCl 2(PMe2Ph) 3(PPhMe)] with Mel) afforded evidence for at least three isomers in solution at low-temperature. The low temperature 31P{1H) n.m.r. spectrum and its 31P-31P DQCOSY spectrum recorded at -75 °C have been analyzed in terms of these conformational isomers. Further investigations of the tetrakis-phosphine complexes [IrCl 2(PMe3)3(PMe2Ph)][C104] and [IrCl 2(PMe3)3(PMePh 2)][C104] also showed the presence of rotational isomers. A controlled synthesis of the cluster [Os 3(|i-H)(|i-PPhH)(CO)10] is reported and the reactions of the anionic phosphinidene cluster [Os 3(|i-H)(p-PPh)(CO)10]‘ with electrophiles are included. Reaction of the anion with methyliodide gave [Os 3(|i-H)(p- PPhMe)(CO)10] characterised crystallographically and found to contain an endo phenyl group indicating inversion of stereochemistry at phosphorus. The crystal structure of [{Os3(|x 3-PPh)(CO) 10)2Hg] is described. - 2- Reaction of the anionic phosphido complex [Mo(CO) 5(PPhH)]' with the metal electrophiles [PtCl 2(dppe)] and [PtCl 2(PEt3)J was seen to be simple nucleophilic substitution at the platinum(II) centres. A single major product isolated from the reaction of the [Mo(CO) 5(PPhH)]‘ with [PtCl 2(dppe)] was isolated. The single-crystal X- ray structure of this compound revealed it to be [Pt(ji-PPhH) 2{Mo(CO)5} 2(dppe)]. 3IP{ XH) n.m.r. studies of this complex confirmed the existence of two diastereoisomers and these have been separated using preparative HPLC techniques. We have also shown that these complexes exist as several rotameric isomers in solution giving rise to broad n.m.r. signals in the 31P{!H} n.m.r. spectrum. The synthesis of [Pt(ji- PPhH )2 { Mo(CO )5 } 2(PPh 2C2H2PPh2)] and [Pt(p-PPh )2 {Mo(CO)4} (dppe)] reinforced the above proposal regarding rotamers in solution and these compounds are observed to occur in both possible diastereoisomeric forms. Three products have been identified from the reaction of [Mo(CO) 5(PPhH)]' with [P tO ^ P E ^ and extensive 31P{1H) n.m.r. investigations carried out. The single-crystal X-ray structures of the two products [Pt(|i- PPhH) { Mo(CO )5 } Cl(PEta)J and rranj-[Pt(p-PPhH) 2{Mo(CO)5)2(PEg2] have been determined. Variable-temperature 31P{!H} n.m.r. studies have shown the former complex to exist in three rotameric forms in solution and these are rapidly exchanging at room temperature. The trinuclear complex [Pt(p-PPhH) 2{Mo(CO)5)2}(PEt3)2] was identified in both cis and trans fonns, the former isomer was identified by n.m.r. methods whilst the single-crystal X-ray structure of the trans isomer was determined. The 31P{1H) n.m.r. spectrum of trans- [Pt(|i-PPhH )2 {Mo(CO)5} 2(PEt3)2] revealed the existence of two diastereiosomeric forms. Table of Contents Abstracts 2 Table of Contents 4 Acknowledgements 11 Chapter 1 Introduction 13 1.1 Preparation and Properties of Phosphine and its Organic Derivatives 14 1.1.1 Preparation of Phosphine 14 1.1.2 Structure and Properties of Phosphine 15 1.1.3 Spectroscopic Characterisation of the Complexes 17 1.1.4 Structural Implication of 31P{*H} N.M.R. Parameters 20 1.2 Structural Survey of Phosphine Ligands and their Derivatives 21 1.2.1 Interaction with One Metal Centre 21 1.2.2 Interaction with Two Metal Centres 24 1.2.3 Interaction with Three Metal Centres 27 1.2.4 Interaction with Four Metal Centres 32 1.2.5 Interaction with more than Four Metal Centres 35 1.3 Related Nitrogen Donor Ligands 37 1.3.1 Amines and Dialkylamides 37 1.3.2 Imides and Nitrides 40 Chapter 2 Thermal Reaction of Phenylphosphine with [Ru3(CO)12] 42 2.1 Introduction 43 - 4- 2.2 Results and Discussion 44 2.2.1 Thermal Reaction of [Ru 3(CO)12] with an excess of Phenylphosphine 44 2.2.2 Mass Spectra of [Ru 3(|i-H)(|X-PPhH) 3(CO)7] 55 2.2.3 Crystal Structure of [Ru3(|i-H)(|i-PPhH) 3(CO)7] 56 2.2.4 Identification of [Ru 3(|i-H)2(|i-PPhH) 2(CO)8] 61 2.2.5 Crystal Structure of [Ru 3(|i-H)2(fx 3-PPh)(PPhH 2)(CO)8] 63 2.2.6 Reaction of [Ru 3(^H )2(^-PPh)(CO)9] 67 2.3 Results Using Cyclohexylphosphine 69 2.3.1 Reaction of [Ru^CO)^ with Cyclohexylphosphine 69 2.3.2 Spectroscopic Characterisation of [Ru 3(p,-H) 2(p,- PCyH)2(CO)8] 69 2.3.3 Spectroscopic Characterisation of [Ru 3(|i-H)(|i- PCyH)3(CO)7] 72 2.3.4 Spectroscopic Charactersiation of [Ru 3(|i-H)2(|i3- PCy)(PCyH2)(CO)8] 77 2.3.5 Mass Spectra of some Phosphido and Phosphinidene Clusters 81 2.3.6 Pyrolysis of [Ru 3(^-H)2(^-PCy)(PCyH2)(CO)8] 81 2.4 Transformation of [Ru 3(ji3-PPh) 2(CO)9] to Higher Nuclearity Clusters 85 2.4.1 Attempted Hydrogenation of [Ru 3(|l-PPh) 2(CO)9] 85 2.4.2 Crystal Structure of [Ru6(p.-H)(p. 3-PPh) 2(|i4-PPh) 2(CO)12] 86 2.4.3 Crystal Structure of [Ru6(|X3-PPh) 2(|i4-PPh) 2(CO)12] 90 2.4.4 Structural Relationship between [RueCm-PPhMiV PPh) 2(CO)12], [Ru6(p.-H) 2([i3-PPh) 2(|i4-PPh) 2(CO)12], and [ R u ^ - P P h ^ - P P h ^ C O ^ 95 2.4.5 *H N.M.R. Studies of [Ru 6(^-PPh) 2(^i4-PPh) 2(CO)u] and [Ru6(|X3-PPh) 2(p. 4-PPh)(CO)12] 105 2.4.6 Attempted Hydrogenation of [Ru 6(|i3-PPh) 2(ji4-PPh) 2(CO)12] 112 2.4.7 Pyrolysis of [Os 6(^-PPh) 2(CO)12] 113 - 5- 2.5 Conclusion 117 2.6 Experimental 119 2.7 Spectroscopic Characterisation of the Complexes 124 Chapter 3 Synthesis of Phosphine and Phosphido Complexes of Iridium(III) 130 3.1 Introduction 131 3.2 Results and Discussion 139 3.2.1 Synthesis of Phosphine Complexes of Iridium(III) 139 3.2.2 Spectroscopic Characterisation of the Complexes [IrCl2(PMe2Ph) 3(PHR1R2)][C104] 140 3.2.3 Attempted Deuteration of [IrCl 2(PMe2Ph) 3(PH3)][C10J 146 3.2.4 Crystal Structure of [hCl 2(PMe2Ph) 3(PPh 2H)][C104] 146 3.3 Synthesis of the Corresponding Phosphido Complexes 151 3.3.1 Deprotonation of [IrCl 2(PMe2Ph) 3(PR1R2H)][C10J 151 3.3.2 Spectroscopic Characterisation of the Phosphido Complexes 152 3.3.3 Structural Considerations 155 3.4 Conclusions 157 3.5 Experimental 158 3.6 Spectroscopic Data for the Complexes 161 Chapter 4 Reactions of Phosphido Complexes of Iridium(III) 164 4.1 Introduction 165 - 6- 4.2 Results and Discussion 172 4.2.1 Reaction with Simple Electrophiles 172 4.2.2 Reaction with Gold Phosphine Chloride Complexes 178 4.2.3 Mass Spectra of [{IiCl 2(PMe2Ph) 3(PH2)}2Au][C10J 179 4.2.4 Crystal Structure of [{IrCl 2(PMe2Ph) 3(PH2)}2Au][C104] 179 4.2.5 Spectroscopic Characteristics 184 4.2.6 Reaction of [Ira 2(PMe2Ph) 3(PHR)] (R = Ph, H) with Organomercury Compounds 191 4.3 Conclusions 194 4.4 Experimental 195 4.5 Spectroscopic data for the Complexes 199 Chapter 5 Conformations of Tetrakis-Phosphine Complexes of Iridium(III) 202 5.1 Introduction 203 5.2 Results and Discussion 207 5.2.1 Synthesis of [IrCl 2(PMe2Ph) 4][C104] 207 5.2.2 Crystal Structure of PrCl 2(PMe2Ph) 4][C104] 209 5.3 N.M.R.
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  • Review of Studies Focused on Heterocyclic Compounds Containing a Heteroatom and Aromaticity Evaluation Methods

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    Bulletin of Environment, Pharmacology and Life Sciences Bull. Env. Pharmacol. Life Sci., Vol 3 [7] June 2014: 108-115 ©2014 Academy for Environment and Life Sciences, India Online ISSN 2277-1808 Journal’s URL:http://www.bepls.com CODEN: BEPLAD Global Impact Factor 0.533 Universal Impact Factor 0.9804 REVIEW ARTICLE Review of Studies Focused on Heterocyclic Compounds Containing a Heteroatom and Aromaticity Evaluation Methods Mojdeh Yousefian Langroudi Department of Chemistry, Organic Branch, Islamic Azad University of Rasht, Rasht, Iran Email: [email protected] ABSTRACT Aromaticity is one of the most important concepts in chemistry and is of particular interest in understanding the structure and properties of heterocyclic compounds. There is still much debate on the subject that which of the reactivity, energy, magnetic and geometric patterns can better assess this feature. On other hand, heterocyclic compounds play an important role in biological processes. Hence, the scientists are trying to understand the chemistry of heterocyclic in order to improve the quality of human life. Structural study of many of these compounds due to limited synthetic methods is difficult; however, using chemical calculations, assessments of sustainability and magnetic properties of many known or unknown heterocyclic compounds would be possible. This study reviews the various criteria of Aromaticity evaluation of heterocyclic compounds containing a common heteroatom at two rings junction to achieve a comprehensive view of these methods. Keywords: Aromaticity, NICS, (HOMO-LUMO)gap, Susceptibility exaltations Received 09.03.2014 Revised 12.04.2014 Accepted 04.06.2014 INTRODUCTION Heterocyclic compounds play an important role in biological processes; hence, the scientists are trying to understand the chemistry of heterocyclic compounds in order to improve the quality of human life [1].
  • Recent Progress Concerning the N-Arylation of Indoles

    Recent Progress Concerning the N-Arylation of Indoles

    molecules Review Review RecentRecent ProgressProgress Concerningconcerning the the NN-Arylation-Arylation of of Indoles Indoles Petr Oeser, Jakub Koudelka, Artem Petrenko and Tomáš Tobrman * Petr Oeser, Jakub Koudelka , Artem Petrenko and Tomáš Tobrman * Department of Organic Chemistry, University of Chemistry and Technology, 16628 Prague, Czech Republic; [email protected] of Organic (P.O.); Chemistry, [email protected] University of Chemistry (J.K.); [email protected] and Technology, 16628 (A.P.) Prague, Czech Republic; [email protected]* Correspondence: (P.O.); [email protected] [email protected] (J.K.); [email protected] (A.P.) * Correspondence: [email protected] Abstract: This review summarizes the current state-of-the-art procedures in terms of the prepara- Abstract:tion of N-arylindoles.This review summarizesAfter a short the intr currentoduction, state-of-the-art the transition-metal procedures-free in procedures terms of the available preparation for oftheN N-arylindoles.-arylation of After indoles a short are briefly introduction, discussed. the Th transition-metal-freeen, the nickel-catalyzed procedures and palladium-catalyzed available for the NN-arylation-arylation ofof indoles are brieflyboth discussed. discussed. In Then,the next the section, nickel-catalyzed copper-catalyzed and palladium-catalyzed procedures for the NN-arylation-arylation ofof indolesindoles areare bothdescribed. discussed. The final In the sectio nextn section,focuses copper-catalyzedon recent findings procedures in the field forof bio- the Nlogically-arylation active of indolesN-arylindoles. are described. The final section focuses on recent findings in the field of biologically active N-arylindoles. Keywords: N-arylation; indole; Buchwald–Hartwig amination; Ullmann condensation; Chan–Lam Keywords:coupling N-arylation; indole; Buchwald–Hartwig amination; Ullmann condensation; Chan– Lam coupling 1.