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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. -
Synthesis of Fused and Bridged Ring Systems James Nicolas Ong Sy Iowa State University
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1988 Synthesis of fused and bridged ring systems James Nicolas Ong Sy Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Sy, James Nicolas Ong, "Synthesis of fused and bridged ring systems " (1988). Retrospective Theses and Dissertations. 9735. https://lib.dr.iastate.edu/rtd/9735 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS The most advanced technology has been used to photo graph and reproduce this manuscript from the microfilm master. UMI films the original text directly from the copy submitted. Thus, some dissertation copies are in typewriter face, while others may be from a computer printer. In the unlikely event that the author did not send UMl a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyrighted material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are re produced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each oversize page is available as one exposure on a standard 35 mm slide or as a 17" x 23" black and white photographic print for an additional charge. -
Organometallic and Catalysis
ORGANOMETALLIC AND CATALYSIS Dr. Malay Dolai, Assistant Professor, Department of Chemistry, Prabhat Kumar College, Contai, Purba Medinipur-721404, WB, India. 1.Introduction Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkaline, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and tin, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide (metal carbonyls), cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. In 1827, Zeise's salt is the first platinum- olefin complex: K[PtCl3(C2H4)].H2O, the first invented organometallic compound. Organometallic compounds find wide use in commercial reactions, both as homogeneous catalysis and as stoichiometric reagents For instance, organolithium, organomagnesium, and organoaluminium compounds, examples of which are highly basic and highly reducing, are useful stoichiometrically, but also catalyze many polymerization reactions. Almost all processes involving carbon monoxide rely on catalysts, notable examples being described as carbonylations. The production of acetic acid from methanol and carbon monoxide is catalyzed via metal carbonyl complexes in the Monsanto process and Cativa process. Most synthetic aldehydes are produced via hydroformylation. The bulk of the synthetic alcohols, at least those larger than ethanol, are produced by hydrogenation of hydroformylation- derived aldehydes. -
1 Equilibria and Thermochemistry
k 1 1 Equilibria and Thermochemistry Answers to Problems Problem 1.1 A hydrocarbon, RH, can be isomerized in reversible reactions into two isomeric compounds P1 and P2 with the same heat of reaction. Both have C1 symmetry. P1 is a rigid molecule, and P2 is a flexible one adopting several conformations of similar stability. Which product will be preferred at equilibrium? Answer Products P1 and P2 equilibrate with RH in reversible reactions at temperature T.Thepreferredproductwillbe T ⇆ T T that for which the free energy of reaction ΔrG (reactants product P1 or P2) =ΔrH − TΔrS is the smallest. T ⇆ T ⇆ T T If ΔrH (RH P1) =ΔrH (RH P2), the product with the largest entropy (S (P1), S (P2)), will be favored at equilibrium at temperature T. Entropy expresses the degree of freedom available to an ensemble of molecules of a given compound. It depends upon the number of different microscopic states available to these molecules, and this depends on the size of the molecules themselves (P1 and P2 have the same molecular weight as they are isomers of the starting material RH), and the energy separation between the microscopic states available to them. k k The microscopic states that contribute most to the entropy are translational and rotational states for which the energy separation between quantum levels are the smallest. A rigid molecule is a molecule that does not equi- librate with several conformers of similar stabilities. It has only one energy minimum along all the coordinates that describe its geometrical deformations, including torsion about its -and-bonds and bond elongation. -
Organo-Transition Metal Chemistry Some Studies
ORGANO-TRANSITION METAL CHEMISTRY SOME STUDIES IN ORGANO-TRANSITION METAL CHEMISTRY By COLIN CRINDROD, B.Sc. A Thesis Submitted to the Faculty of Graduate Studies in Partial Fulfilment of the Requirements for the Degree Master of Science McMaster University October 1966 MASTER OF SCIENCE (1966) MCMASTER UNIVERSITY (Chemistry) Hamilton, Ontario TITLE: Some Studies in Organo-Transition Metal Chemistry AUTHOR: Colin Grindrod, B.Sc. (Manchester University) SUPERVISOR: Dr. P. M. Maitlis NUMBER OF PAGES: iv, 71 SCOPE AND CONTENTS: The work described is an extension of the ligand-transfer reactions of substituted cyclobutadienes and cyclopentadienyls previously carried out by Maitlis et al. Efforts were directed particularly to ligand transfer reactions of n-allyl-transition metal complexes. The reactions of organic halides with metal carbonyls were also studied in attempts to isolate new organometallic derivatives. (ii) ACKNOWLEDGEMENTS The author wishes to express his sincere gratitude for the stimulating advice and constant encouragement provided by Dr. P. M. Maitlis, under whose guidance this work was carried out. Thanks are also extended to Imperial Oil Co. Ltd. for providing the financial support which made this study possible. (iii) CONTENTS Page INTRODUCTION Historical................................... 1 Cyclobutadiene-transition metal oompeeees... 7 Ligand-transfer reactions................... 10 Allyl-transition metal complexes............ 13 Reactions of metal carbonyls with organic halides.... ..................... 25 DISCUSSION -
Metal Carbonyls
MODULE 1: METAL CARBONYLS Key words: Carbon monoxide; transition metal complexes; ligand substitution reactions; mononuclear carbonyls; dinuclear carbonyls; polynuclear carbonyls; catalytic activity; Monsanto process; Collman’s reagent; effective atomic number; 18-electron rule V. D. Bhatt / Selected topics in coordination chemistry / 2 MODULE 1: METAL CARBONYLS LECTURE #1 1. INTRODUCTION: Justus von Liebig attempted initial experiments on reaction of carbon monoxide with metals in 1834. However, it was demonstrated later that the compound he claimed to be potassium carbonyl was not a metal carbonyl at all. After the synthesis of [PtCl2(CO)2] and [PtCl2(CO)]2 reported by Schutzenberger (1868) followed by [Ni(CO)4] reported by Mond et al (1890), Hieber prepared numerous compounds containing metal and carbon monoxide. Compounds having at least one bond between carbon and metal are known as organometallic compounds. Metal carbonyls are the transition metal complexes of carbon monoxide containing metal-carbon bond. Lone pair of electrons are available on both carbon and oxygen atoms of carbon monoxide ligand. However, as the carbon atoms donate electrons to the metal, these complexes are named as carbonyls. A variety of such complexes such as mono nuclear, poly nuclear, homoleptic and mixed ligand are known. These compounds are widely studied due to industrial importance, catalytic properties and structural interest. V. D. Bhatt / Selected topics in coordination chemistry / 3 Carbon monoxide is one of the most important π- acceptor ligand. Because of its π- acidity, carbon monoxide can stabilize zero formal oxidation state of metals in carbonyl complexes. 2. SYNTHESIS OF METAL CARBONYLS Following are some of the general methods of preparation of metal carbonyls. -
The Use of Iron Carbonyl Complexes in Organic
THE USE OF IRON CARBONYL COMPLEXES IN ORGANIC SYNTHESIS a thesis presented by GARY DAVID ANNIS in partial fulfilment of the requirements for the award of the degree of DOCTOR OF PHILOSOPHY OF THE UNIVERSITY OF LONDON WHIFFEN LABORATORY CHEMISTRY DEPARTMENT IMPERIAL COLLEGE LONDON SW7 2AY. AUGUST/ 1979. 1. CONTENTS page ABSTRACT 3 ACKNOWLEDGEMENTS 5 INTRODUCTION 6 1. CARBONYL INSERTION REACTIONS 8 (a)Sodium Tetracarbonylferrates 8 (b)Sodium Hydridotetracarbonylferrates 13 (c)Lithium Acyl Iron Complexes 14 (d)Magnesium Acyl Iron Complexes 15 (e)Potassium Tetracarbonylferrates 16 (f)Miscellaneous Ferrates 17 CARBONYL INSERTION REACTIONS USING DICARBONYL- PENTAHAPTOCYCLOPENTADIENYL IRON COMPLEXES 20• CARBONYL INSERTION REACTIONS USING IRON CARBONYLS 25 (a)Reactions of Simple Vinyl Cyclopropanes with Iron Carbonyls 25 (b)The Reactions of More Complex Hydrocarbons with Iron Carbonyls 33 (c)Diene Complexes of Iron Carbonyls 38 (d)The Reaction of Hetero Systems with Iron Carbonyls 46 (e)Coupling of Olefins using Iron Carbonyls 52 2. RING FORMING REACTIONS USING IRON CARBONYLS 55 3. FUNCTIONAL GROUP REMOVAL AND REDUCTION USING IRON CARBONYLS 58 4. ISOMERISATION AND REARRANGEMENTS USING IRON CARBONYLS 61 2. page 5. OTHER METHODS OF C—C BOND FORMATION USING IRON CARBONYLS 62 6. FUNCTIONAL GROUP PROTECTION USING IRON CARBONYLS 64 7. ACTIVATION OF ALKENES USING IRON CARBONYLS 66 REFERENCES 67 RESULTS AND DISCUSSION 77 Preparation of Lactones from Ferrolactones 78 Mass Spectral and N.m.r. Data of the Ferrolactones 99 Mechanism of Formation of Ferrolactones 104 Mechanism of the Oxidation of Ferrolactones 106 Structure of Iron Carbonyl Complexes 110 Preparation of Lactams from Ferrolactams 115 Mechanism for Formation and Oxidation of Ferrolactams 122 Preparation of NH Lactams 123 Miscellaneous Chemistry 126 EXPERIMENTAL 130 REFERENCES 162 3. -
Download This Article PDF Format
Dalton Transactions View Article Online PERSPECTIVE View Journal | View Issue Synthesis of organometallic pentalenide complexes Cite this: Dalton Trans., 2019, 48, 5107 Stuart M. Boyt, a Niko A. Jenek a and Ulrich Hintermair *a,b While a number of reports have established the unique structures and electronic properties of mono- and dinuclear pentalenide complexes of s, p, d and f block elements, access to these intriguing compounds is Received 15th February 2019, restricted by synthetic challenges. Here we review various strategies for the synthesis, functionalisation Accepted 12th March 2019 and (trans)metalation of pentalenide complexes from a practical point of view, pointing out promising DOI: 10.1039/c9dt00689c avenues for future research that may allow wider access to novel pentalenide complexes for application in rsc.li/dalton many different areas. units isolated from each other by a cyclobutane linkage 1. Introduction 2 Creative Commons Attribution 3.0 Unported Licence. (Fig. 1). Pentalene (Pn,C8H6) has long fascinated theoretical and syn- Due to its inherent instability, Pn itself is of limited use for thetic organic chemists for its anti-aromatic 8π system.1 Unlike applications in synthetic chemistry.† However, similar to other π π the flexible 8 cyclooctatetraene (COT,C8H8) Pn is planar due 8 anti-aromatics like COT, double reduction of Pn to pentale- 2− 2− to its bicyclic ring structure, enforcing its anti-aromaticity. As a nide (Pn ,C8H6 ) generates a stable 10π aromatic system result, it readily dimerises above −196 °C to form two fulvene that presents itself as a useful π ligand for organometallic chemistry.4 Its dianionic nature makes it a stronger donor for Lewis-acidic metals than neutral 10π hydrocarbons such as This article is licensed under a aDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. -
Dissertation
CO-Sources for the Liberation of Cellular Messenger Molecules Dissertation Zur Erlangung des akademischen Grades doctor rerum naturalium (Dr. rer. nat.) vorgelegt dem Rat der Chemisch-Geowissenschaftlichen Fakultät der Friedrich-Schiller-Universität Jena von Master-Chem. Taghreed Jazzazi geboren am 16.07.1985 in Amman/Jordan 1. Gutachter: Prof. Dr. Matthias Westerhausen, FSU Jena 2. Gutachter: Prof. Dr. Rainer Beckert, FSU Jena Tag der öffentlichen Verteidigung: 12. June 2013 2 DEDICATIONS To Candles of my life, my husband Father and Mother My Brother and Sisters All my Family With Love i Table of Contents Dedication…………………………………………………………………………… i Table of Contents………………………………………………………………….... ii List of Figures……………………………………………………………………….. v List of Schemes……………………………………………………………………... ix List of Tables…………………………………………………………........................ xi Chapter One 1. Introduction 1 1.1 Carbon monoxide (CO)…………………………………………………. 1 1.2 Carbonyl chemistry …………………………………………………....... 2 1.2.1 Metal carbonyl complexes ……………………………………………... 2 1.2.2 Preparation of metal carbonyl complexes ……………………………. 4 1.2.3 Reaction of metal carbonyl complexes ……………………………….. 5 1.2.4 Coordination modes of carbonyl ligands in metal carbonyl 8 complexes.......................................................................................... 1.3 Carbon monoxide (CO) releasing molecules (CORMs)..................... 10 1.3.1 CORMs in general ……………………………..................................... 10 1.3.2 Some selected CORMs ………………………………………………… 11 1.3.2.1 Molybdenum CORMs…………………………………………………… -
Iron(III) As Lewis Acid Catalyst in Organosilicon and Carbonyl Chemistry
Risto Savela Iron(III) as Lewis Acid Catalyst in Organosilicon and Carbonyl Chemistry Iron(III) as Lewis Acid Catalyst in Organosilicon and Carbonyl Chemistry Acid Catalyst in Organosilicon Iron(III) as Lewis Risto Savela Johan Gadolin Process Chemistry Centre Laboratory of Organic Chemistry Faculty of Science and Technology Åbo Akademi University ISBN 978-952-12-3205-3 Åbo, Finland Painosalama Oy – Turku, Finland 2015 2015 2015 Iron(III) as Lewis Acid Catalyst in Organosilicon and Carbonyl Chemistry Risto Savela Johan Gadolin Process Chemistry Centre Laboratory of Organic Chemistry Faculty of Science and Technology Åbo Akademi University Åbo, Finland 2015 Supervisor and Custos Professor Reko Leino Laboratory of Organic Chemistry Åbo Akademi University Åbo, Finland Opponent Dr. George Britovsek Department of Chemistry Imperial College London London, United Kingdom Reviewers Professor Timo Repo Laboratory of Inorganic Chemistry University of Helsinki Helsinki, Finland and Professor Hans Adolfsson Department of Organic Chemistry Stockholm University Stockholm, Sweden ISBN 978-952-12-3206-0 Painosalama Oy – Turku, Finland 2015 Remember kids, the only difference between screwing around and science, is writing it down. Adam Savage PREFACE The present work was carried out at the Laboratory of Organic Chemistry, Department of Natural Sciences, Åbo Akademi University between the years 2009 and 2015. Financial support from the former National Graduate School of Organic Chemistry and Chemical Biology, Stiftelsen för Åbo Akademi, Magnus Ehrnrooth foundation, Orion Farmos Research foundation, Rector of Åbo Akademi and Kemian Päivien säätiö is gratefully acknowledged. I wish to express my gratitude to my supervisor Professor Reko Leino for giving me the opportunity to join the research group, giving me a chance to venture into the world of iron catalysis and for his patience and support during these years. -
Signature Redacted - C Department Pf Chem.Istry
"The Synthesis and Reactivity of Thiolate Bridged Diiron Hexacarbonyl Complexes" by JEFFREY BARMONT HOKE B.S., The Pennsylvania State University (1983) SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY June 1987 c Massachusetts Institute of Technology 1987 Signature of Auth@ Signature redacted - C Department pf Chem.istry Certified by Signature redacted $iitmar Seyferth Thesis Supervisor Accepted by Sign ature redacted Glenn'A. Berchtold, Chairman Departmental Committee on Graduate Students MASSACHUSE ITS NS: j7 OF TECHNOLOC3Y LIBRARMES Archives -2- This doctoral thesis has been examined by a Committee of the Department of Chemistry as follows: Professor Alan Davison Signature redacted Chairman Professor Dietmar Seyferth1. Signature redacted Th L&sAs Superviq Professor Richard R. Schrock Signature redacted -3- This Thesis is Dedicated with love to my wife, Elaine, and to my parents -4- "The Synthesis and Reactivity of Thiolate Bridged Diiron Hexacarbonyl Complexes" by Jeffrey Barmont Hoke Submitted to the Department of Chemistry on May 22, 1987 in partial fulfillment of the requirements for the Degree of Doctor of Philosophy ABSTRACT Chapter 1: 2 "Synthesis of (p-RlC=NR )(p-RS)Fe 2 (CO) 6 " New p-iminoacyl complexes of the type (p-RlC=NPh)(p- RS)Fe 2 (CO) 6 were prepared from the reactions of triiron dodecacarbonyl with thioimidates (RlC(SR)=NR2 ). The geome- try of the bridging iminoacyl and thiolate ligands was determined primarily from IR and 1 3 C NMR spectral correlations to related acyl and thioacyl systems. In related work, reaction of [Et 3 NH][(p-CO)(p-RS)Fe 2 (CO) 6 ] with N-phenyl benzimidoyl chloride was found to be an alternate and superior route to complexes of this class. -
9'3 __Ithesis Supervisor
The Organometallic Chemistry of Ambident Acetone Dianions. Reactions with Group 4 and 14 Element Dihalides. By Tao Wang B.S., Chemistry Hefei Polytechnic University, 1982 M.S., Chemistry Southern Methodist University, 1990 Submitted to the Department of Chemistry in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the Massachusetts Institute of Technology February !9'3 © Massachusetts Institute of Technology 1995 All rights reserved. Signature of Author -"- Department of Chemistry November 14, 1994 Certified by / / n X Dietmar Seyferth __IThesis Supervisor Accepted by I / v // Dietmar Seyferth, Chairman Departmental Committee on Graduate Students rrsE@e~.sli 2 This doctoral thesis has been examined by a Committee of the Department of Chemistry as follows: Professor Hans-Conrad zur Loye _I _ Chairman .N r9 I Professor Dietmar Seyferth - ~~~/ Thesis Supervisor A9 Professor Richard R. Schrock 3 The Organometallic Chemistry of Ambident Acetone Dianions. Reactions with Group 4 and 14 Element Dihalides. By Tao Wang Submitted to the Department of Chemistry on November 14, 1994 in partial fulfillment of the requirement for the degree of Doctor of Philosophy ABSTRACT Chapter One. Reactions of Group 4 Metallocene Dichlorides with Acetone Dianions 2 - Acetone dianions, [CH2C(O)CR 2] (R = Ph, H) react with group 4 metallocene dichlorides (M = Zr, Hf) as C, O dinucleophiles. The products in solution are (by VPO) monomeric 2-metallaoxa-3-methylenecyclobutanes, but in the solid state they are "dimers", 1,5-dimetalla-2,6-dioxa-3,7-dimethylenecyclooctanes. The structure of 1,1,5,5- tetrakis(rl 5 -cyclopentadienyl)-3,7-bis(diphenylmethylene)- 1,5-dizircona-2,6- dioxacycloocetane was determined by X-ray crystallography.