DOCSLIB.ORG

Synthesis, Characterization, and Reactivity Studies of Low-Valent 3D Metal Complexes With

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis, Characterization, and Reactivity Studies of Low-Valent 3D Metal Complexes With Institut für Anorganische Chemie Synthesis, Characterization, and Reactivity Studies of Low-valent 3d Metal Complexes with N-Heterocyclic Carbene and α-Diimine Ligands Dissertation Zur Erlangung des Doktorgrades der Naturwissenschaften Dr. rer. nat. an der Fakultät Chemie und Pharmazie der Universität Regensburg vorgelegt von: Stefan Pelties aus Nordhorn Regensburg 2016 Der experimentelle Teil der vorliegenden Arbeit wurde in der Zeit zwischen November 2012 und Februar 2016 unter Anleitung von Prof. Dr. Robert Wolf am Institut für Anorganische Chemie der Universität Regensburg und unter Anleitung von Prof. Dr. Michael K. Whittlesey am Department of Chemistry, University of Bath, UK (Juni 2015 und Juli 2016) angefertigt. Die Arbeit wurde angeleitet von: Prof. Dr. Robert Wolf Promotionsgesuch eingereicht am: 17.03.2016 Tag der mündlichen Prüfung: 02.05.2016 Promotionsausschuss: Vorsitz Prof. Dr. Olga Garcia Mancheño Erstgutachter Prof. Dr. Robert Wolf Zweitgutachter Prof. Dr. Manfred Scheer Dritter Prüfer Prof. Dr. Axel Jacobi von Wangelin Prologue This thesis reports on the synthesis and characterization of reactive 3d metal complexes with N-heterocyclic carbene (NHC) and α-diimine ligands. Chapter 1 reviews the chemistry of mononuclear phosphane and NHC nickel(I) complexes. Besides the synthesis and structural motifs of the nickel(I) radicals, this chapter also deals with the reactivity of these species. In chapter 2-5 the synthesis, characterization, and reactivity studies of monomeric NHC nickel(I) complexes is discussed. Chapter 6 covers the synthesis and structural characterization of iron(II), cobalt(II), and nickel(II) complexes with a cyclic (alkyl)(amino)carbene ligand. Investigations concerning the synthesis and characterization of NHC manganese(II) complexes is reported in chapter 7. In chapter 8 the synthesis, characterization, and first reactivity studies of a highly reduced cobalt complex with an α-diimine ligand is discussed. The final chapter 9 summarizes the results of this thesis and gives a brief outlook. Table of Contents 1 The Chemistry of Mononuclear Phosphane and N-Heterocyclic Carbene……………….1 Nickel(I) Complexes: Synthesis, Structural Motifs, and Reactivity 1.1 Introduction…………………………………………………………………………....1 1.2 General Synthetic Access…………………………………………………………........2 1.3 Nickel(I) Phosphane Complexes…………………………………………………….....3 1.3.1 Mononuclear Phosphane Nickel(I) Halides and Related Cationic Nickel(I)…………..3 Complexes with Weakly Coordinating Counteranions 1.3.2 Mononuclear Nickel(I) Phosphane Complexes with Ancillary N-Donors………….....7 1.3.3 Pincer Complexes……………………………………………………………………..10 1.3.4 Mononuclear Nickel(I) Complexes with Additional S-Donor Ligands……………....12 1.3.5 Piano Stool Complexes with Cyclobutadiene and Cyclopentadienyl Ligands……….14 1.4 Mononuclear N-Heterocyclic Carbene Nickel(I) Complexes………………………...16 1.5 Conclusion……………………………………………………………………………21 2 Selective P 4 Activation by an Organometallic Nickel(I) Radical: Formation of a………31 Dinuclear Nickel(II) Tetraphosphide and Related Di- and Trichalcogenides 2.1 Introduction…………………………………………………………………………..33 2.2 Results and Discussion……………………………………………………………….34 2.3 Conclusion…………………………………………………………………………....38 2.4 Supporting Information……………………………………………………………....41 2.4.1 General Procedures…………………………………………………………………..41 2.4.2 Synthesis of [ (C 5H5)NiCl(IMes)]……………………………………………………41 2.4.3 Synthesis of [ (C 5H5)Ni(IDipp)] ( 1)………………………………………………….41 2.4.4 Synthesis of [ (C 5H5)Ni(IMes)] ( 2)…………………………………………………..42 2.4.5 Synthesis of [(C 5Me 5)Ni(IDipp)] ( 3)………………………………………………....43 2.4.6 Synthesis of [ (C 5H5)Ni(SPh)(IDipp)] ( 4)……………………………………………44 2.4.7 Synthesis of [(C 5H5)Ni(TEMPO)(IDipp)] ( 5)………………………………………..44 1 1 2.4.8 Synthesis of [ (C 5H5)Ni(IDipp) 2(µ-η :η -S2)] ( 6-S) and……………………………...45 1 1 [(C 5H5)Ni(IDipp) 2(µ-η :η -S3)] ( 7-S) 1 1 2.4.9 Synthesis of [ (C 5H5)Ni(IDipp) 2(µ-η :η -Se 2)] ( 6-Se )………………………………..46 1 1 2.4.10 Synthesis of [ (C 5H5)Ni(IDipp) 2(µ-η :η -Te 2)] ( 6-Te )……………………………….46 1 1 2.4.11 Synthesis of [ (C 5H5)Ni(IDipp) 2(µ-η :η -P4)] ( 8)…………………………………….47 2.4.12 Synthesis of 1-H……………………………………………………………………..48 2.4.13 Synthesis of 1-THF ………………………………………………………………….48 2.5 X-ray Crystallography…………………………………………………………….....49 2.6 EPR Spectroscopy………………………………………………………………..….54 2.7 Electrochemical Measurements………………………………………………...……56 3 Half-Sandwich Nickel(I) Complexes of Ring-Expanded N-Heterocyclic Carbenes:……61 A Structural and Quantum Chemical Study 3.1 Introduction…………………………………………………………………………...63 3.2 Results and Discussion………………………………………………………………..65 3.3 Conclusion……………………………………………………………………………70 3.4 Supporting Information……………………………………………………………….71 3.4.1 General Procedures……………………………………………………………………71 3.4.2 [CpNiBr(6-Mes)] ( 1Br )……………………………………………………………….71 3.4.3 [CpNi(6-Mes)] ( 1)…………………………………………………………………….72 3.4.4 [CpNiBr(7-Mes)] ( 2Br )……………………………………………………………….73 3.4.5 [CpNi(7-Mes)] ( 2)…………………………………………………………………….74 3.4.6 [CpNiBr(6-MesDAC)] ( 3Br )…………………………………………………………75 3.4.7 [CpNi(6-MesDAC)] ( 3)……………………………………………………………….76 3.4.8 X-ray Crystallography………………………………………………………………...78 3.4.5 DFT: Cartesian Coordinates of 1, 2, and 3……………………………………………81 4 Formation of Heteronickelacycles through the Reductive Coupling of Phenyl…………89 Iso(thio)cyanate 4.1 Introduction…………………………………………………………………………..91 4.2 Results and Discussion……………………………………………………………….92 4.3 Conclusion…………………………………………………………………………....96 4.4 Supporting Information………………………………………………………………99 4.4.1 General Procedures…………………………………………………………………..99 4.4.2 Synthesis of [(IDipp)NiSC(NPh)N(Ph)CS] ( 1)……………………………………...99 4.4.3 Synthesis of [(IDipp)NiN(Ph)C(O)CH 2CH(Ph) ( 3)…………………………………101 4.4.4 X-ray Crystallography………………………………………………………………103 4.4.5 DFT: Cartesian Coordinates of 3…………………………………………………….105 5 Insertion of Phenyl Isothiocyanate into a P−P Bond of a Nickel-substituted………….109 Bicyclo[1.1.0]tetraphosphabutane 5.1 Introduction…………………………………………………………………………111 5.2 Results and Discussion……………………………………………………………....113 5.3 Conclusion…………………………………………………………………………..117 5.4 Supporting Information……………………………………………………………...121 5.4.1 General Procedures………………………………………………………………......121 5.4.2 Synthesis of 1Mes ……………………………………………………………………..121 5.4.3 Synthesis of 2a ……………………………………………………………………....123 5.4.4 Synthesis of 2b ……………………………………………………………………....125 5.4.5 X-ray Crystallography……………………………………………………………….133 5.4.6 Computational Details……………………………………………………………….135 6 Synthesis and Structural Characterization of Iron(II), Cobalt(II), and Nickel(II)……147 Complexes of a Cyclic (Alkyl)(amino)carbene 6.1 Introduction…………………………………………………………………………149 6.2 Results and Discussion……………………………………………………………...151 6.3 Conclusion…………………………………………………………………………..154 6.4 Supporting Information……………………………………………………………...155 6.4.1 General Procedures…………………………………………………………………..155 6.4.2 Synthesis of [FeCl( µ-Cl)(CAAC 1)] 2 (1)……………………………………………..155 6.4.3 Synthesis of [CoBr( µ-Br)(CAAC 1)] 2 (2)…………………………………………….155 6.4.4 Synthesis of [NiBr( µ-Br)(CAAC 1)] 2 (3)…………………………………………….156 6.4.5 X-ray Crystallography……………………………………………………………….157 7 Preparation of a Trigonal Planar Manganese(II) Amido Complex Supported by an…161 N-Heterocyclic Carbene 7.1 Introduction…………………………………………………………………………163 7.2 Results and Discussion………………………………………………………………165 7.3 Conclusion…………………………………………………………………………..169 7.4 Supporting Information……………………………………………………………...170 7.4.1 General Procedures………………………………………………………………….170 7.4.2 Synthesis of [MnCl( µ-Cl)(IDipp)] 2 (1)………………………………………………170 7.4.3 Synthesis of [(IDipp)Mn{N(SiMe 3)2}2] ( 3)………………………………………….171 7.4.4 X-ray Crystallography……………………………………………………………….172 8 Synthesis and Reactivity Studies of a Heteroleptic α-Diimine Cobalt Anion………….175 8.1 Introduction…………………………………………………………………………177 8.2 Results and Discussion………………………………………………………………179 8.2.1 Synthesis and Characterisation………………………………………………………179 8.2.2 Reactivity Studies of 1 with Carbon Disulfide and tert -Butylphosphalkyne…181 8.2.3 Selective P 4 Activation by 1…………………………………………………..183 8.2.4 UV-Vis and NIR Spectrocopy……………………………………………………….185 8.2.5 Cyclic Voltammetry…………………………………………………………..186 8.2.6 Chemical Oxidation of the Dianion 4……………………………………………….187 8.3 Conclusion…………………………………………………………………………..190 8.4 Supporting Information……………………………………………………………...196 8.4.1 General Procedures………………………………………………………………….196 8.4.2 Synthesis of [K(OEt 2)][Co(BIAN)(cod)] ( 1)………………………………………...196 8.4.3 Synthesis of [K(thf) 2]2[{(BIAN)Co} 2(µ-C2S4)] ( 2)………………………………….198 8.4.4 Synthesis of [K(thf) 3][Co(BIAN)(P 2C2tBu)] ( 3)…………………………………….199 4 4 8.4.5 Synthesis of [K(thf)] 2[{(BIAN)Co} 2(µ-η :η -P4)] ( 4)……………………………….201 4 4 8.4.6 Synthesis of [K(OEt 2)][{(BIAN)Co} 2(µ-η :η -P4)] ( 5)………………………...202 8.5 X-ray Crystallography………………………………………………………………204 8.6 UV-Vis Spectrum of 1 and Vis-NIR Spectra of 1−4…………………………………206 8.7 Cyclic Voltammetry…………………………………………………………………209 9 Summary…………………………………………………………………………………..213 10 Acknowledgement………………………………………………………………………...223 11 Curriculum Vitae…………………………………………………………………………225 12 List of Publications………………………………………………………………………..226 Chapter 1. The Chemistry of Mononuclear Phosphane and NHC Ni(I) Complexes 1 The Chemistry of Mononuclear Phosphane and N-Heterocyclic Carbene Nickel(I) Complexes: Synthesis, Structural Motifs, and Reactivity 1.1 Introduction Although the importance of nickel(I) species in catalytic cycles has been recognized early, 1 much of the literature pays particular attention to the chemistry
Load more

Recommended publications
  • Perspectives on How Nature Employs the Principles of Organometallic Chemistry in Dihydrogen Activation in Hydrogenases†
    4682 Organometallics 2010, 29, 4682–4701 DOI: 10.1021/om100436c Perspectives on How Nature Employs the Principles of Organometallic Chemistry in Dihydrogen Activation in Hydrogenases† John C. Gordon* and Gregory J. Kubas* Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States Received May 6, 2010 Relatively recent developments in metalloenzyme and organometallic chemistry have targeted a growing link between these outwardly incongruous fields, giving birth to a merger now popularly termed “bio-organometallic” chemistry. The astonishing discovery of CO and CN ligands bound to dinuclear iron sites in billion-year-old hydrogenase enzymes has led to a new paradigm and triggered an explosion of research on bioinspired chemistry. The article will focus on the impressive array of organometallic chemistry principles that work in concert in the structure and function of H2ases. Molecular H2 is at the forefront of bioinspired energy, and its production and storage are critical for renewable energy systems. Biomimetic inorganic chemistry and photochemistry involving water splitting for H2 production has erupted in the past decade and will also be reflected upon here. I. Introduction be despised and avoided by nature. This view was shattered by the relatively recent discovery, initially spectroscopically2,3 then At the macroscopic level, nature displays dazzling beauty crystallographically,4 of CO and CN ligands bound to dinuclear and surprises on a regular basis. On the molecular level, its iron sites in hydrogenase (H2ase) enzymes that have existed in mystique is even more fascinating to biologists and chemists numerous microorganisms for over a billion years. It is now in all their subfields.
    [Show full text]
  • N-Heterocyclic Carbenes (Nhcs)
    Baran Lab N - H e t e r o c y c l i c C a r b e n e s ( N H C s ) K. J. Eastman An Introduction to N-heterocyclic Carbenes: How viable is resonance contributer B? Prior to 1960, a school of thought that carbenes were too reactive to be smaller isolated thwarted widespread efforts to investigate carbene chemistry. base ! N N N N R R R R Perhaps true for the majority of carbenes, this proved to be an inaccurate X- assessment of the N-heterocyclic carbenes. H longer Kirmse, W. Angerw. Chem. Int. Ed. 2004, 43, 1767-1769 In the early 1960's Wanzlick (Angew. Chem. Int. Ed. 1962, 1, 75-80) first investigated the reactivity and stability of N-heterocyclic carbenes. Attractive Features of NHCs as Ligands for transition metal catalysts: Shortly thereafter, Wanzlick (Angew. Chem. Int. Ed. 1968, 7, 141-142) NHCs are electron-rich, neutral "#donor ligands (evidenced by IR frequency of reported the first application of NHCs as ligands for metal complexes. CO/metal/NHC complexes). Surprisingly, the field of of NHCs as ligands in transition metal chemistry Electron donating ability of NHCs span a very narrow range when compared to remained dormant for 23 years. phosphine ligands In 1991, a report by Arduengo and co-workers (J. Am. Chem. Soc. 1991, Electronics can be altered by changing the nature of the azole ring: 113, 361-363) on the extraodinary stability, isolation and storablility of benzimidazole<imidazole<imidazoline (order of electron donating power). crystalline NHC IAd. NHC-metal complex stability: NaH, DMSO, MeOH N N N N + H2 + NaCl NHCs form very strong bonds with the majority of metals (stronger than Cl- phosphines!) H IAd N-heterocyclic carbenes are electronically (orbital overlap) and sterically (Me vs.
    [Show full text]
  • Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc
    Metal-Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc Richard H. Duncan Lyngdoh*,a, Henry F. Schaefer III*,b and R. Bruce King*,b a Department of Chemistry, North-Eastern Hill University, Shillong 793022, India B Centre for Computational Quantum Chemistry, University of Georgia, Athens GA 30602 ABSTRACT: This survey of metal-metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) n+ the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) , (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging.
    [Show full text]
  • Cyclopentadienyl Compounds of the First Row Transition Metals And
    University of Vermont ScholarWorks @ UVM Graduate College Dissertations and Theses Dissertations and Theses 2017 Cyclopentadienyl Compounds of the First Row Transition Metals and Early Actinides: Novel Main-Group Bond Forming Catalysis and New Metallacycles Justin Kane Pagano University of Vermont Follow this and additional works at: https://scholarworks.uvm.edu/graddis Part of the Chemistry Commons Recommended Citation Pagano, Justin Kane, "Cyclopentadienyl Compounds of the First Row Transition Metals and Early Actinides: Novel Main-Group Bond Forming Catalysis and New Metallacycles" (2017). Graduate College Dissertations and Theses. 700. https://scholarworks.uvm.edu/graddis/700 This Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks @ UVM. It has been accepted for inclusion in Graduate College Dissertations and Theses by an authorized administrator of ScholarWorks @ UVM. For more information, please contact [email protected]. CYCLOPENTADIENYL COMPOUNDS OF THE FIRST ROW TRANSITION METALS AND EARLY ACTINIDES: NOVEL MAIN-GROUP BOND FORMING CATALYSIS AND NEW METALLACYCLES A Dissertation Presented by Justin Kane Pagano to The Faculty of the Graduate College of The University of Vermont In Partial Fulfilment of the Requirements For the Degree of Doctor of Philosophy Specializing in Chemistry May, 2017 Defense Date: November 29, 2016 Dissertation Examination Committee: Rory Waterman, Ph. D., Advisor John M. Hughes, Ph. D., Chairperson Matthias Brewer, Ph. D. Jaqueline L. Kiplinger, Ph. D. Matthew D. Liptak, Ph. D. Cynthia J. Forehand, Ph. D., Dean of the Graduate College ABSTRACT Cyclopentadienyl first row transition-metal compounds have been well studied 5 since the 1950’s, with the nearly ubiquitous CpFe(CO)2Me (FpMe) (Cp = η -C5H5) being one of the first organometallics to be fully characterized.
    [Show full text]
  • Download This Article PDF Format
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Nickel-catalyzed cyclization of alkyne-nitriles with organoboronic acids involving anti- Cite this: Chem. Sci.,2016,7,5815 carbometalation of alkynes† Xingjie Zhang, Xin Xie and Yuanhong Liu* A nickel-catalyzed regioselective addition/cyclization of o-(cyano)phenyl propargyl ethers with arylboronic acids has been developed, which provides an efficient protocol for the synthesis of highly functionalized Received 16th March 2016 1-naphthylamines with wide structural diversity. The reaction is characterized by a regioselective and Accepted 19th May 2016 anti-addition of the arylboronic acids to the alkyne and subsequent facile nucleophilic addition of the DOI: 10.1039/c6sc01191h resulting alkenylmetal to the tethered cyano group. Mechanistic studies reveal that a Ni(I) species might www.rsc.org/chemicalscience be involved in the catalytic process. to an exo-alkene upon cyclization3,4 (Scheme 1, eqn (1)). Creative Commons Attribution 3.0 Unported Licence. Introduction Cyclizations involving the regioselective formation of the Transition-metal-catalyzed cascade reactions consisting of alkenylmetal with a metal a-to the R1 substituent such as syn-B 5 multiple carbometalation steps have attracted considerable are quite rare (Scheme 1, eqn (2)), possibly because the attention in organic synthesis since these processes enable the subsequent cyclization process will involve a highly strained rapid assembly of complex structures in an efficient, atom- transition state. Thus,
    [Show full text]
  • Synthesis and Reactivity of Cyclopentadienyl Based Organometallic Compounds and Their Electrochemical and Biological Properties
    Synthesis and reactivity of cyclopentadienyl based organometallic compounds and their electrochemical and biological properties Sasmita Mishra Department of Chemistry National Institute of Technology Rourkela Synthesis and reactivity of cyclopentadienyl based organometallic compounds and their electrochemical and biological properties Dissertation submitted to the National Institute of Technology Rourkela In partial fulfillment of the requirements of the degree of Doctor of Philosophy in Chemistry by Sasmita Mishra (Roll Number: 511CY604) Under the supervision of Prof. Saurav Chatterjee February, 2017 Department of Chemistry National Institute of Technology Rourkela Department of Chemistry National Institute of Technology Rourkela Certificate of Examination Roll Number: 511CY604 Name: Sasmita Mishra Title of Dissertation: ''Synthesis and reactivity of cyclopentadienyl based organometallic compounds and their electrochemical and biological properties We the below signed, after checking the dissertation mentioned above and the official record book(s) of the student, hereby state our approval of the dissertation submitted in partial fulfillment of the requirements of the degree of Doctor of Philosophy in Chemistry at National Institute of Technology Rourkela. We are satisfied with the volume, quality, correctness, and originality of the work. --------------------------- Prof. Saurav Chatterjee Principal Supervisor --------------------------- --------------------------- Prof. A. Sahoo. Prof. G. Hota Member (DSC) Member (DSC) ---------------------------
    [Show full text]
  • Expedient Syntheses of the N-Heterocyclic Carbene Precursor Imidazolium Salts Ipr·Hcl, Imes·Hcl and Ixy·Hcl
    Expedient syntheses of the N-heterocyclic carbene precursor imidazolium salts IPr·HCl, IMes·HCl and IXy·HCl Lukas Hintermann Full Research Paper Open Access Address: Beilstein Journal of Organic Chemistry 2007, 3, No. 22. Institute of Organic Chemistry, RWTH Aachen University, Landoltweg doi:10.1186/1860-5397-3-22 1, D-52074 Aachen, Germany Received: 25 June 2007 Email: Accepted: 28 August 2007 Lukas Hintermann - [email protected] Published: 28 August 2007 © 2007 Hintermann; licensee Beilstein-Institut License and terms: see end of document. Abstract The 1,3-diaryl-imidazolium chlorides IPr·HCl (aryl = 2,6-diisopropylphenyl), IMes·HCl (aryl = 2,4,6-trimethylphenyl) and IXy·HCl (aryl = 2,6-dimethylphenyl), precursors to widely used N-heterocyclic carbene (NHC) ligands and catalysts, were prepared in high yields (81%, 69% and 89%, respectively) by the reaction of 1,4-diaryl-1, 4-diazabutadienes, paraformaldehyde and chloro- trimethylsilane in dilute ethyl acetate solution. A reaction mechanism involving a 1,5-dipolar electrocyclization is proposed. Background Imidazolylidene carbenes have been investigated as ligands in coordination chemistry, as powerful steering/controlling elements in transition-metal catalysis,[1,2] and more recently as metal-free catalysts for organic reactions[3,4]. Some prominent members of the family of N-heterocyclic carbenes (NHC) are the sterically encumbered imidazolylidenes IPr and IMes (Figure 1), which can also be considered as analogues of bulky and electron-rich tertiary phosphanes. In contrast to the latter, their synthesis does not involve air-sensitive or pyrophoric organometallic reagents, and they are conveniently stored and used in the form of their air-stable precursors, namely the imidazolium salts IPr·HCl (1,3-bis-{2,6- diisopropylphenyl}imidazolium chloride; 1) or IMes·HCl (1,3- bis-{2,4,6-trimethylphenyl}imidazolium chloride; 2) (Figure 1).
    [Show full text]
  • Ne1~~L~------¥", ~ ~1:C SYNTHESIS and CHA.H.ACTEHIZATION of GROUP IB and IIB METAL COMPLEXES with DITBRTIARY PHOSPHINE and DITERTIARY ARSINE LIGANDS
    YOUf JGSTCJ\i,7l STATE Uf H\'ERSITi GRADUATE SCHOOL THESIS Submitt ed in Partial Fu.l..fillment c,f the Rcquh·er:'..ents For th.e Degree elf Master of Science TITLE Synthesis and Characterization of Group IB and IIB Metal Complexes with Ditertiary Phosphine and Ditertiary Arsine Ligands PRESENTED BY Raj al M. Vyas ACCEPTED BY TI -iE DEPARTMENT OF Chemistry 'fief"1t dlli~~~l1r.~;~~i~---------,l~~_(ll~ 1 ne1~~l~------¥", ~ ~1:c SYNTHESIS AND CHA.H.ACTEHIZATION OF GROUP IB AND IIB METAL COMPLEXES WITH DITBRTIARY PHOSPHINE AND DITERTIARY ARSINE LIGANDS by Raj al M. "Vyas Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in the Chemistry Program n1"'t 2 S l~ 72' Adviser Date Dean Youngstown State University June, 1 972 ii ABSTRACT SYNTHESIS AND CHARACTERIZATION OF G.nOUP IB AND IIB METAL COMPLEXES WITH DITERTIARY PHOSPHINE AND DITERTIAY ARSINE LIGANDS Rajal M. Vyas Master of Sci~nce in Chemistry Youngstown State University, 1972 This investigation describes the preparation and properties of complexes of the metals copper, silver, gold, zinc, cadmium, mercury, and nickel with di tertiary phos­ phine and ditertiary arsine ligands. The experimental work done is described in three parts: (a) Triphenylphosphine complexes. Some of these have been reported in the literature. Triphenylphosphine complexes of zinc, mercury, copper, and silver have been made either in the molten state1 by heating a mixture of metal halides and triphenylphosphine, or by mixing hot alcoholic solutions of the reactants. 2 Analytical infor­ mation is either completely lacking or at best is only partially reported.
    [Show full text]
  • Transition Metal Complexes of Ambiphilic Ligands
    TRANSITION METAL COMPLEXES OF AMBIPHILIC LIGANDS Ph.D. Thesis Bradley E. Cowie Department of Chemistry and Chemical Biology McMaster University LATE TRANSITION METAL COMPLEXES OF GROUP 13 LEWIS ACID- CONTAINING AMBIPHILIC LIGANDS By BRADLEY E. COWIE, H.B.Sc A Thesis Submitted to the School of Graduate Studies in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy McMaster University © Copyright by Bradley E. Cowie, October, 2015. Ph.D. Thesis Bradley E. Cowie Department of Chemistry and Chemical Biology McMaster University McMaster University DOCTOR OF PHILOSOPHY (2015) Hamilton, Ontario (CHEMISTRY) TITLE: Late transition Metal Complexes of Group 13 Lewis Acid-Containing Ambiphilic Ligands AUTHOR: Bradley E. Cowie SUPERVISOR: Prof. David J. H. Emslie NUMBER OF PAGES: lii, 380 ii Ph.D. Thesis Bradley E. Cowie Department of Chemistry and Chemical Biology McMaster University Lay Abstract Ambiphilic ligands are defined as ligands which contain both conventional Lewis basic donors and unconventional Lewis acidic moieties, and the focus of this thesis is to expand the transition metal chemistry of Group 13 Lewis acid-containing ambiphilic ligands. This work expands the knowledge base of fundamental coordination and organometallic chemistry by exploring the effects of ambiphilic ligands on the structures, stability and reactivity of the resulting late transition metal complexes. Three different ambiphilic ligand systems have been employed in this research (TXPB, FcPPB and FcPPAl), which vary either by the structural rigidity of the ligand backbone (TXPB = thioxanthene; FcPPB and FcPPAl = ferrocene), the donor groups available to bind to the metal centre (TXPB = phosphine/thioether; FcPPB and FcPPAl = phosphine/phosphine), or the identity of the appended Lewis acid (TXPB and FcPPB = aryldiphenylborane; FcPPAl = aryldimethylalane).
    [Show full text]
  • Supporting Information
    Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2016 Supporting Information 1 Table of contents 1. Synthetic procedures ....................................................................................................................... 3 1.1 General remarks ........................................................................................................................ 3 1.2 General table ............................................................................................................................. 4 1.2.1 General table for the synthesis of [CuCl(NHC)] ................................................................. 5 1.2.2 General table for the synthesis of [Cu(NHC)2]Y (Y = BF4 or PF6) ........................................ 7 1.3 Imidazolium salts synthesis ....................................................................................................... 9 1.4 [CuCl(NHC)] synthesis .............................................................................................................. 18 1.5 [Cu(NHC)2]Y (Y = BF4 or PF6) synthesis ..................................................................................... 22 2. Influence of reagent stoichiometry for the production of [CuCl(IMes)] ....................................... 27 2.1 Influence of copper stoichiometry .......................................................................................... 27 2.2 Influence of dioxygen stoichiometry .....................................................................................
    [Show full text]
  • NHC and Nucleophile Chelation Effects on Reactive Iron(Ii) Species in Alkyl
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue NHC and nucleophile chelation effects on reactive iron(II) species in alkyl–alkyl cross-coupling† Cite this: Chem. Sci.,2018,9,1878 Valerie E. Fleischauer,‡ Salvador B. Munoz˜ III,‡ Peter G. N. Neate, William W. Brennessel and Michael L. Neidig * While iron–NHC catalysed cross-couplings have been shown to be effective for a wide variety of reactions (e.g. aryl–aryl, aryl–alkyl, alkyl–alkyl), the nature of the in situ formed and reactive iron species in effective catalytic systems remains largely undefined. In the current study, freeze-trapped Mossbauer¨ spectroscopy, and EPR studies combined with inorganic synthesis and reaction studies are utilised to define the key in situ formed and reactive iron–NHC species in the Kumada alkyl–alkyl cross-coupling of (2-(1,3-dioxan-2-yl) ethyl)magnesium bromide and 1-iodo-3-phenylpropane. The key reactive iron species formed in situ is identified as (IMes)Fe((1,3-dioxan-2-yl)ethyl)2, whereas the S ¼ 1/2 iron species previously identified in this chemistry is found to be only a very minor off-cycle species (<0.5% of all iron). Reaction and kinetic studies demonstrate that (IMes)Fe((1,3-dioxan-2-yl)ethyl)2 is highly reactive towards the electrophile Creative Commons Attribution-NonCommercial 3.0 Unported Licence. À1 resulting in two turnovers with respect to iron (kobs > 24 min ) to generate cross-coupled product with overall selectivity analogous to catalysis. The high resistance of this catalytic system to b-hydride elimination of the alkyl nucleophile is attributed to its chelation to iron through ligation of carbon and one oxygen of the acetal moiety of the nucleophile.
    [Show full text]
  • Transmetalation Between Au(I) and Sn(IV) Complexes
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Archivio Ricerca Ca'Foscari Inorganica Chimica Acta 404 (2013) 105–112 Contents lists available at SciVerse ScienceDirect Inorganica Chimica Acta journal homepage: www.elsevier.com/locate/ica Transmetalation between Au(I) and Sn(IV) complexes. The reaction mechanism in non-coordinating and coordinating polar solvents ⇑ Luciano Canovese a, , Carlo Levi a, Fabiano Visentin a, Claudio Santo a, Valerio Bertolasi b a Dipartimento di Scienze Molecolari e Nanosistemi, University Ca’ Foscari, Venice, Italy b Dipartimento di Chimica and Centro di Strutturistica Diffratometrica, Univesrsity of Ferrara, Ferrara, Italy article info abstract Article history: Some novel gold(I) derivatives of the type [LAuCl] (L = DIC, PPh3, NHCs) have been synthesized and char- Received 4 March 2013 acterized. The products of the transmetalation reaction between these species and tributyl-phenylethy- Received in revised form 15 April 2013 nylstannane have been isolated and characterized. An exhaustive kinetic study on the transmetalation Accepted 17 April 2013 reaction has also been carried out in CHCl and CH CN. The experimental results were discussed in terms Available online 26 April 2013 3 3 of the electronic and steric characteristics of the ligands and an interpretation of the peculiar influence of different solvents on the reaction rates was proposed. Keywords: Ó 2013 Elsevier B.V. All rights reserved. Transmetalation reaction Gold(I) carbene complexes Kinetic study Tributyl-phenylethynylstannane 1. Introduction diazonium salts [7]. We have chosen the aforementioned gold(I) complexes since we already had some experience on such ligands Recently, the peculiar behavior of gold complexes as homoge- and complexes in insertion and oxidative addition reactions [8].
    [Show full text]