Ne1~~L~------¥", ~ ~1:C SYNTHESIS and CHA.H.ACTEHIZATION of GROUP IB and IIB METAL COMPLEXES with DITBRTIARY PHOSPHINE and DITERTIARY ARSINE LIGANDS
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An Earlier Collection of These Notes in One PDF File
UNIVERSITY OF THE WEST INDIES MONA, JAMAICA Chemistry of the First Row Transition Metal Complexes C21J Inorganic Chemistry http://wwwchem.uwimona.edu.jm/courses/index.html Prof. R. J. Lancashire September 2005 Chemistry of the First Row Transition Metal Complexes. C21J Inorganic Chemistry 24 Lectures 2005/2006 1. Review of Crystal Field Theory. Crystal Field Stabilisation Energies: origin and effects on structures and thermodynamic properties. Introduction to Absorption Spectroscopy and Magnetism. The d1 case. Ligand Field Theory and evidence for the interaction of ligand orbitals with metal orbitals. 2. Spectroscopic properties of first row transition metal complexes. a) Electronic states of partly filled quantum levels. l, ml and s quantum numbers. Selection rules for electronic transitions. b) Splitting of the free ion energy levels in Octahedral and Tetrahedral complexes. Orgel and Tanabe-Sugano diagrams. c) Spectra of aquated metal ions. Factors affecting positions, intensities and shapes of absorption bands. 3. Magnetic Susceptibilities of first row transition metal complexes. a) Effect of orbital contributions arising from ground and excited states. b) Deviation from the spin-only approximation. c) Experimental determination of magnetic moments. Interpretation of data. 4. General properties (physical and chemical) of the 3d transition metals as a consequence of their electronic configuration. Periodic trends in stabilities of common oxidation states. Contrast between first-row elements and their heavier congeners. 5. A survey of the chemistry of some of the elements Ti....Cu, which will include the following topics: a) Occurrence, extraction, biological significance, reactions and uses b) Redox reactions, effects of pH on the simple aqua ions c) Simple oxides, halides and other simple binary compounds. -
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. -
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. -
Boron and Titanium(IV) Halide Mediated Reactions
University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 8-2010 Boron and Titanium(IV) Halide Mediated Reactions Michael Patrick Quinn University of Tennessee - Knoxville, [email protected] Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Organic Chemistry Commons Recommended Citation Quinn, Michael Patrick, "Boron and Titanium(IV) Halide Mediated Reactions. " PhD diss., University of Tennessee, 2010. https://trace.tennessee.edu/utk_graddiss/908 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Michael Patrick Quinn entitled "Boron and Titanium(IV) Halide Mediated Reactions." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a major in Chemistry. George W. Kabalka, Major Professor We have read this dissertation and recommend its acceptance: Shane Foister, Ziling (Ben) Xue, Paul Dalhaimer Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) To the Graduate Council: I am submitting herewith a dissertation written by Michael Patrick Quinn entitled ―Boron and Titanium(IV) Halide Mediated Reactions.‖ I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a major in Chemistry. -
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. -
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. -
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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, -
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) --------------------------- -
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). -
Crystal Structure Transformations in Binary Halides
1 A UNITED STATES DEPARTMENT OF A111D3 074^50 IMMERCE JBLICAT10N NSRDS—NBS 41 HT°r /V\t Co^ NSRDS r #C£ DM* ' Crystal Structure Transformations in Binary Halides u.s. ARTMENT OF COMMERCE National Bureau of -QC*-| 100 US73 ho . 4 1^ 72. NATIONAL BUREAU OF STANDARDS 1 The National Bureau of Standards was established by an act of Congress March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation’s science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research and provides: (1) a basis for the Nation’s physical measure- ment system, (2) scientific and technological services for industry and government, (3) a technical basis for equity in trade, and (4) technical services to promote public safety. The Bureau consists of the Institute for Basic Standards, the Institute for Materials Research, the Institute for Applied Technology, the Center for Computer Sciences and Technology, and the Office for Information Programs. THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United States of a complete and consistent system of physical measurement; coordinates that system with measurement systems of other nations; and furnishes essential services leading to accurate and uniform physical measurements throughout the Nation’s scien- tific community, industry, and commerce. The Institute consists of a Center for Radia- tion Research, an Office of Measurement Services and the following divisions: Applied Mathematics—Electricity—Heat—Mechanics—Optical Physics—Linac Radiation 2—Nuclear Radiation 2—Applied Radiation 2—Quantum Electronics 3— Electromagnetics 3—Time and Frequency 3—Laboratory Astrophysics 3—Cryo- 3 genics . -
Chemical Redox Agents for Organometallic Chemistry
Chem. Rev. 1996, 96, 877−910 877 Chemical Redox Agents for Organometallic Chemistry Neil G. Connelly*,† and William E. Geiger*,‡ School of Chemistry, University of Bristol, U.K., and Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 Received October 3, 1995 (Revised Manuscript Received January 9, 1996) Contents I. Introduction 877 A. Scope of the Review 877 B. Benefits of Redox Agents: Comparison with 878 Electrochemical Methods 1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 The authors (Bill Geiger, left; Neil Connelly, right) have been at the forefront of organometallic electrochemistry for more than 20 years and have had 1. Radical Cations 891 a long-standing and fruitful collaboration. 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich 894 Neil Connelly took his B.Sc. (1966) and Ph.D. (1969, under the direction Compounds of Jon McCleverty) degrees at the University of Sheffield, U.K. Post- 4. Quinones 895 doctoral work at the Universities of Wisconsin (with Lawrence F. Dahl) 5. Other Organic Oxidants 896 and Cambridge (with Brian Johnson and Jack Lewis) was followed by an appointment at the University of Bristol (Lectureship, 1971; D.Sc. degree, III. Reductants 896 1973; Readership 1975). His research interests are centered on synthetic A. Inorganic 896 and structural studies of redox-active organometallic and coordination 1. -
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).