Inorganic Chemistry Model Paper –I Time: 3 Hours Max Marks: 70 Instructions: 1) the Question Paper Has Two Parts
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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. -
Crystal Field Theory (CFT)
Crystal Field Theory (CFT) The bonding of transition metal complexes can be explained by two approaches: crystal field theory and molecular orbital theory. Molecular orbital theory takes a covalent approach, and considers the overlap of d-orbitals with orbitals on the ligands to form molecular orbitals; this is not covered on this site. Crystal field theory takes the ionic approach and considers the ligands as point charges around a central metal positive ion, ignoring any covalent interactions. The negative charge on the ligands is repelled by electrons in the d-orbitals of the metal. The orientation of the d orbitals with respect to the ligands around the central metal ion is important, and can be used to explain why the five d-orbitals are not degenerate (= at the same energy). Whether the d orbitals point along or in between the cartesian axes determines how the orbitals are split into groups of different energies. Why is it required? The valence bond approach could not explain the Electronic spectra, Magnetic moments, Reaction mechanisms of the complexes. Assumptions of CFT: 1. The central Metal cation is surrounded by ligand which contain one or more lone pair of electrons. 2. The ionic ligand (F-, Cl- etc.) are regarded as point charges and neutral molecules (H2O, NH3 etc.) as point dipoles. 3. The electrons of ligand does not enter metal orbital. Thus there is no orbital overlap takes place. 4. The bonding between metal and ligand is purely electrostatic i.e. only ionic interaction. The approach taken uses classical potential energy equations that take into account the attractive and repulsive interactions between charged particles (that is, Coulomb's Law interactions). -
CO2 Derivatives of Molecular Tin Compounds. Part 1: † Hemicarbonato and Carbonato Complexes
inorganics Review CO2 Derivatives of Molecular Tin Compounds. Part 1: y Hemicarbonato and Carbonato Complexes Laurent Plasseraud Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB), UMR-CNRS 6302, Université de Bourgogne Franche-Comté, 9 avenue A. Savary, F-21078 Dijon, France; [email protected] Paper dedicated to Professor Georg Süss-Fink on the occasion of his 70th birthday. y Received: 31 March 2020; Accepted: 24 April 2020; Published: 29 April 2020 Abstract: This review focuses on organotin compounds bearing hemicarbonate and carbonate ligands, and whose molecular structures have been previously resolved by single-crystal X-ray diffraction analysis. Most of them were isolated within the framework of studies devoted to the reactivity of tin precursors with carbon dioxide at atmospheric or elevated pressure. Alternatively, and essentially for the preparation of some carbonato derivatives, inorganic carbonate salts such as K2CO3, Cs2CO3, Na2CO3 and NaHCO3 were also used as coreagents. In terms of the number of X-ray structures, carbonate compounds are the most widely represented (to date, there are 23 depositions in the Cambridge Structural Database), while hemicarbonate derivatives are rarer; only three have so far been characterized in the solid-state, and exclusively for diorganotin complexes. For each compound, the synthesis conditions are first specified. Structural aspects involving, in particular, the modes of coordination of the hemicarbonato and carbonato moieties and the coordination geometry around tin are then described and illustrated (for most cases) by showing molecular representations. Moreover, when they were available in the original reports, some characteristic spectroscopic data are also given for comparison (in table form). -
Werner-Type Complexes of Uranium(III) and (IV) Judith Riedhammer, J
pubs.acs.org/IC Article Werner-Type Complexes of Uranium(III) and (IV) Judith Riedhammer, J. Rolando Aguilar-Calderon,́ Matthias Miehlich, Dominik P. Halter, Dominik Munz, Frank W. Heinemann, Skye Fortier, Karsten Meyer,* and Daniel J. Mindiola* Cite This: Inorg. Chem. 2020, 59, 2443−2449 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: Transmetalation of the β-diketiminate salt [M]- Me Ph + Me Ph− − [ nacnac ](M =NaorK; nacnac = {PhNC(CH3)}2CH ) with UI3(THF)4 resulted in the formation of the homoleptic, Me Ph octahedral complex [U( nacnac )3](1). Green colored 1 was fully characterized by a solid-state X-ray diffraction analysis and a combination of UV/vis/NIR, NMR, and EPR spectroscopic studies as well as solid-state SQUID magnetization studies and density functional theory calculations. Electrochemical studies of 1 revealed this species to possess two anodic waves for the U(III/IV) and U(IV/V) redox couples, with the former being chemically accessible. Using mild oxidants, such as [CoCp2][PF6]or [FeCp ][Al{OC(CF ) } ], yields the discrete salts [1][A] (A = − 2 3 −3 4 PF6 , Al{OC(CF3)3}4 ), whereas the anion exchange of [1][PF6] with NaBPh4 yields [1][BPh4]. Me Dipp μ 12 ■ INTRODUCTION UCl3(THF)] and [{( nacnac )UCl}2( 2-Cl)3]Cl. In Me Dipp− ’ some cases, disubstitution of nacnac generates the Alfred Werner s disapproval of the complex ion-chain theory Me Dipp η3 Me Dipp 13 proposed by Jørgensen and Blomstrand,1 via the introduction rearranged species [( nacnac )( - nacnac )UI], of coordination complexes and the concept of Nebenvalenz,1,2 where one ligand has changed hapticity, most likely due to fi steric constraints. -
Of Grignard Reagent Formation. the Surface Nature of the Reaction
286 Ace. Chem. Res. 1990,23, 286-293 Mechanism of Grignard Reagent Formation. The Surface Nature of the Reaction H. M. WALBORSKY Dittmer Laboratory of Chemistry, Florida State University, Tallahassee, Florida 32306 Received February 23, 1990 (Revised Manuscript Received May 7, 1990) The reaction of organic halides (Br, C1, I) with mag- Scheme I nesium metal to yield what is referred to today as a Kharasch-Reinmuth Mechanism for Grignard Reagent Grignard reagent has been known since the turn of the Formation century,' The name derives from its discoverer, Nobel (1)(Mg0)AMg*)2y + RX 4 [(M~'~(MQ')~~-,('MQX)+ R.] + laureate Victor Grignard. How this reagent is formed, (Mgo)x-2(MQ')2~MgX)(MgR) that is, how a magnesium atom is inserted into a car- bon-halogen bond, is the subject of this Account. ('4 (Ms0),-*(M9')2~MgX)(MgR) + + (Mg0)x-dMg*)2y+2 + 2RMgX RX + Mg - RMgX Kharasch and Reinmuth,, persuaded by the work of late under the same conditions gave Itl = 6.2 X s-l. Another system that meets the above criterion is the Gomberg and Bachmad as well as by product analyses of many Grignard formation reactions that existed in vinyl system. The lack of reactivity of vinyl halides toward SN1reactions is well-known and is exemplified the literature prior to 1954,speculated that the reaction involved radicals and that the radical reactions might by the low solvolysis rate of 2-propenyl triflate5 in 80% involve "surface adherent radicals, at least in part". The ethanol at 25 OC, kl being 9.8 X s-l. -
M.Sc. (Chemistry) M
Regulations 2019 Curriculum and Syllabi (Amendments updated upto June 2020) M.Sc. (Chemistry) M. Sc. Chemistry Regulations 2019 REGULATIONS 2019 CURRICULUM AND SYLLABI (Amendments updated upto June 2020) M.Sc. CHEMISTRY B.S. Abdur Rahman Crescent Institute of Science and Technology 1 M. Sc. Chemistry Regulations 2019 B.S. Abdur Rahman Crescent Institute of Science and Technology 2 M. Sc. Chemistry Regulations 2019 VISION AND MISSION OF THE INSTITUTION VISION B.S.Abdur Rahman Crescent Institute of Science and Technology aspires to be a leader in Education, Training and Research in multidisciplinary areas of importance and to play a vital role in the Socio-Economic progress of the Country in a sustainable manner. MISSION To blossom into an internationally renowned Institute. To empower the youth through quality and value-based education. To promote professional leadership and entrepreneurship. To achieve excellence in all its endeavors to face global challenges. To provide excellent teaching and research ambience. To network with global Institutions of Excellence, Business, Industry and Research Organizations. To contribute to the knowledge base through Scientific enquiry, Applied Research and Innovation. B.S. Abdur Rahman Crescent Institute of Science and Technology 3 M. Sc. Chemistry Regulations 2019 B.S. Abdur Rahman Crescent Institute of Science and Technology 4 M. Sc. Chemistry Regulations 2019 DEPARTMENT OF CHEMISTRY VISION AND MISSION VISION To blossom as a department with excellence in the field of Chemical Sciences through academic and research programmes in cutting-edge areas. MISSION To provide knowledge and skill in Chemical Sciences through post graduate and doctoral programmes. To undertake research in emerging areas of Chemical Sciences and transform the findings for the benefit of the society. -
Limitation of Crystal Field Theory the Main Drawback of the Crystal Field Theory Is That It Does Not Consider the Covalent Character in Metal-Ligand Bonding at All
CHAPTER 7 Metal-Ligand Bonding: Limitation of Crystal Field Theory The main drawback of the crystal field theory is that it does not consider the covalent character in metal-ligand bonding at all. It treats the metal-ligand interaction in a purely electrostatic framework which is pretty far from reality. All the effects which originate from covalence cannot be explained by this theory. Therefore, the main limitations of crystal field theory can be concluded only after knowing the causes and magnitude of the covalence in the metal-ligand bonds. Evidences for the Covalent Character in Metal–Ligand Bond The crystal field theory considers the metal center as well as surrounding ligands as point charges and assumes that the interaction between them is 100% ionic. However, quite strong experimental evidences have proved that there is some covalent character too which cannot be ignored. Some of those experimental evidences are as follows: 1. The nephelauxetic effect: The electrons present in the partially filled d-orbitals of the metal center repel each other to produce a number of energy levels. The placement of these levels on the energy scale depends upon the arrangement of filled electrons. The energy of these levels can be given in terms of “Racah parameters” B and C (a measure of interelectronic repulsion). The energy difference between same multiplicity states is expressed in B and Dq while between different multiplicity states is given in term of B, Dq and C. It has been observed that the complexation of metal center always results in a decrease in interelectronic repulsion parameters which in turn also advocates a decrease in the repulsion between d-electron density. -
Organometallic Chemistry BASIC PRINCIPLES, APPLICATIONS, and a FEW CASE STUDIES
Safety Moment TYLER LAB GROUP MEETING 1 Safety Moment TYLER LAB GROUP MEETING 2 Metal Hydrides: Benchtop vs. Box Hydride = :H- Hydrides are powerful Lewis bases and reducing agent ◦ Exothermically form H2 (this should scare you) ◦ Heating leads to faster reactivity ◦ H evolution leads to rapid increase in pressure2 ◦ Uncontrolled reactions easily cause runaway exotherm, class D fire, explosion, and death/unemployment LiAlH is the #1 chemical cause of fatality in chemical4 industry 3 Metal Hydrides: “I want to commit the murder I was imprisoned for†.” LiAlH4 ◦ Insanely irritating (serious safety hazard) ◦ Extremely moisture sensitive (don’t leave out for >2 minutes) ◦ Ethereal mixtures are pyrophoric! DiBuAl-H ◦ Pyrophoric – it will explode upon exposure to oxygen NaEt3BH ◦ Pyrophoric in solution LiH and NaH ◦ Can be handled on the benchtop (not >2 minutes) ◦ Parrafin oil dispersions much safer KH ◦ Pyrophoric if not in a dispersion ◦ Handle with extreme care! † Sirius Black, Harry Potter and the Prisoner of Azkaban 4 Metal Hydrides: “I want to commit the murder I was imprisoned for†.” CaH2 ◦ Very safe to handle on the benchtop Pt-H, Pd-H, Ni-H ◦ All very pyrophoric NaBH4 ◦ Very safe in general Other hydrides ◦ Treat as pyrophoric ◦ Transition metal hydrides vary in hydridic strength ◦ General rule of thumb: if it does hydrogenations, it is probably pyrophoric ◦ If they’re in organics of any kind, they are probably pyrophoric † Sirius Black, Harry Potter and the Prisoner of Azkaban 5 Organometallic Chemistry BASIC PRINCIPLES, APPLICATIONS, -
Submitted to the Requirements For
THE SYNTIIE$IS OP C LABELLED 2, 4-DICI LOROi-EENOÇYAGETIC ACID by ERNEST GEORGE AWORSKI A THESIS submitted to OREGON STA1 COLLEGE in partial fulfillment or the requirements for the degree of MAS2R 0F SCIENCE June 1950 PROVED: professor ot Clie'thlstry Department In Charge of Major Head of Department of' Chemistry Chairman of School Graduate Conimittee Dean of Graduate School Date thesis is presented Typed by Clara Homyar ACNOWLEDGMNTS The author wishes to express his appreciation to Dr. oseph S. Butts for his eneouragem.ent and generous direction in r4laking this work possible. Grateful aoknowledgnient is given to Dr. Albert V. Logan for his assistance in methodical diff i- culties. This research project was supported by an Atoniic inergy Commission grant carried under Navy contract N7-onr-3 7602. TABLE OF CONTENTS Page I. INTRODUCTION I II. STNTHESI OF ALPHA METH'LENB LABELLED2,14-D . , * 4 A. Apparatus ......*,*., B Method . 7 C. Analysis and }hysica1 Constants 3.7 In. StfliSIs OF C CABBOXTh LABELLED 2LD 19 A. Apparatus . 19 B )kethoc3. , , , , , 23. C. Analysis and PhjsLoa3. Constants 26 Iv DISCUSSION . , , . , , V. SUL2&RY . e e . 30 LTTERATUREOITED .......... 31 I1N1)I. 3 2 THE SYNTHESIS OF C LABELLED 2, 4-DICHLOROHENOXThCETIC ACID I. INTRODUCTION The synthesis or C labelled 2,4-dichlorophen- oxyacetic acid (hereafter referred to as 2,4V-D) was undertaken In order to study the process by which lt exerts its selective herbicidal effect on soiae noxious plants. Should this method prove fruitful, it would be useful for a more systematic approach to the study of ooitounds having potential herbicidal properties. -
Part I. Inversion of Secondary Cyclic Grignard Reagents
This dissertation has been , 69-11,692 microfilmed exactly as received PECHHOLD, Engelbert, 1933- STUDIES OF THE BEHAVIOR AND GENERATION OF GARB ANIONS: PART I. INVERSION OF SECONDARY CYCLIC GRIGNARD REAGENTS. PART II. FRAGMENTATION OF AZOFORMATE SALTS AND ACYLAZO COMPOUNDS WITH BASES. The Ohio State University, Ph.D., 1968 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan ©Copyright "by- Engelbert Pechhold 1969 STUDIES OF THE BEHAVIOR MD GENERATION OF CARBANIONS PART I. INVERSION OF SECONDARY CYCLIC GRIGNARD REAGENTS PART II. FRAGMENTATION OF AZOFORMATE SADIS AND ACYLAZO COMPOUNDS WITH BASES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Engelbert Pechhold * # # * * # The Ohio State University 1968 Approved by •pV-gpa.-t— Adviser Department of Chemistry DEDICATION To my wife, Ingrid, and my parents, whose love, understanding, and encouragement have made this venture possible. ii ACKNOWLEDaEMElWS I -wish to express my deepest appreciation to Professor Gideon Fraenkel for suggestinf^ this problem, and for his guidance and encouragement throughout the course of this research. His assistance in the preparation of this dissertation is gratefully acknowledged. It is an understatement to say that without his un usual courage of conviction and high standards for academic perfor mance, this work could not have come into being. I owe special debt of gratitude to my colleagues for many suimtü-ating discussions of chemical matters and otherwise. In particular, I wish to express my gratitute to Dr. Don Dix, Dr. Dave Mams, and James Morton, who gave me much insight in ny research. -
Organometallics Study Meeting H.Mitsunuma 1
04/21/2011 Organometallics Study Meeting H.Mitsunuma 1. Crystal field theory (CFT) and ligand field theory (LFT) CFT: interaction between positively charged metal cation and negative charge on the non-bonding electrons of the ligand LFT: molecular orbital theory (back donation...etc) Octahedral (figure 9-1a) d-electrons closer to the ligands will have a higher energy than those further away which results in the d-orbitals splitting in energy. ligand field splitting parameter ( 0): energy between eg orbital and t2g orbital 1) high oxidation state 2) 3d<4d<5d 3) spectrochemical series I-< Br-< S2-< SCN-< Cl-< N -,F-< (H N) CO, OH-< ox, O2-< H O< NCS- <C H N, NH < H NCH CH NH < bpy, phen< NO - - - - 3 2 2 2 5 5 3 2 2 2 2 2 < CH3 ,C6H5 < CN <CO cf) pairing energy: energy cost of placing an electron into an already singly occupied orbital Low spin: If 0 is large, then the lower energy orbitals(t2g) are completely filled before population of the higher orbitals(eg) High spin: If 0 is small enough then it is easier to put electrons into the higher energy orbitals than it is to put two into the same low-energy orbital, because of the repulsion resulting from matching two electrons in the same orbital 3 n ex) (t2g) (eg) (n= 1,2) Tetrahedral (figure 9-1b), Square planar (figure 9-1c) LFT (figure 9-3, 9-4) - - Cl , Br : lower 0 (figure 9-4 a) CO: higher 0 (figure 9-4 b) 2. Ligand metal complex hapticity formal chargeelectron donation metal complex hapticity formal chargeelectron donation MR alkyl 1 -1 2 6-arene 6 0 6 MH hydride 1 -1 2 M MX H 1 -1 2 halogen 1 -1 2 M M -hydride M OR alkoxide 1 -1 2 X 1 -1 4 M M -halogen O R acyl 1 -1 2 O 1 -1 4 M R M M -alkoxide O 1-alkenyl 1 -1 2 C -carbonyl 1 0 2 M M M R2 C -alkylidene 1 -2 4 1-allyl 1 -1 2 M M M O C 3-carbonyl 1 0 2 M R acetylide 1 -1 2 MMM R R C 3-alkylidine 1 -3 6 M carbene 1 0 2 MMM R R M carbene 1 -2 4 R M carbyne 1 -3 6 M CO carbonyl 1 0 2 M 2-alkene 2 0 2 M 2-alkyne 2 0 2 M 3-allyl 3 -1 4 M 4-diene 4 0 4 5 -cyclo 5 -1 6 M pentadienyl 1 3. -
High Spin Or Low Spin?
Central Tenants of Crystal Field Theory • The metals (Lewis acids) have d orbitals that are partially filled with electrons. • Ligands, that are Lewis bases with lone pairs, come in and form a covalent bond. • Electrostatic repulsion between the ligand lone pairs with the d-orbital subshell leads to higher energies • Each metal orbital will either be stabilized or destabilized depending on the amount of orbital overlap with the ligand. CFT (Octahedron) (dz2, dx2-y2) Orbitals point directly at ligands eg stronger repulsion dx2y2 E dz2 higher energy (dxy, dyz, dxz) Orbitals point between ligands t2g dxy dyz dxz weaker repulsion lower energy Energy Levels of d-Orbitals in an Octahedron • crystal field splitting energy = • The size of is determined by; metal (oxidation state; row of metal, for 5d > 4d >> 3d) ligand (spectrochemical series) Spectrochemical Series eg eg t2g t2g 3+ [Cr(H2O)6] Greater I < Br < Cl < F < OH < H2O < NH3 < en < NO2 < CN < CO Small Δ Large Δ Weak Field Strong Field Weak M-L interactions Strong M-L interactions How Do the Electrons Go In? • Hund’s rule: one electron each in lowest energy orbitals first • what happens from d4 to d7? d6 Crystal Field Spin Pairing Splitting vs. Δ P High Spin vs. Low Spin Co3+ (d6) High Spin Low Spin Δ < P Δ > P High Spin vs. Low Spin Configurations High Spin vs. Low Spin Configurations high spin low spin d4 3d metal 3d metal weak field strong field ligand d5 ligand 4d & 5d 6 d always d7 What About Other Geometries? linear (CN = 2) z y x tetrahedral (CN = 4) z y x square planar (CN = 4) z how do the electrons on the d orbitals y interact with the ligands in these cases? x Tetrahedral vs.