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A Novel Series of Titanocene Dichloride Derivatives: Synthesis, Characterization and Assessment of Their
A novel series of titanocene dichloride derivatives: synthesis, characterization and assessment of their cytotoxic properties by Gregory David Potter A thesis submitted to the Department of Chemistry in conformity with the requirements for the degree of Doctor of Philosophy Queen’s University Kingston, Ontario, Canada May, 2008 Copyright © Gregory David Potter, 2008 Abstract Although cis-PtCl2(NH3)2 (cisplatin) has been widely used as a chemotherapeutic agent, its use can be accompanied by toxic side effects and the development of drug resistance. Consequently, much research has been focused on the discovery of novel transition metal compounds which elicit elevated cytotoxicities coupled with reduced toxic side effects and non-cross resistance. Recently, research in this lab has focused on preparing derivatives of titanocene dichloride (TDC), a highly active chemotherapeutic agent, with pendant alkylammonium groups on one or both rings. Earlier results have demonstrated that derivatives containing either cyclic or chiral alkylammonium groups had increased cytotoxic activities. This research therefore investigated a new series of TDC complexes focusing specifically on derivatives bearing cyclic and chiral alkylammonium groups. A library of ten cyclic derivatives and six chiral derivatives were synthesized and fully characterized. These derivatives have undergone in vitro testing as anti-tumour agents using human lung, ovarian, and cervical carcinoma cell lines (A549, H209, H69, H69/CP, A2780, A2780/CP and HeLa). These standard cell lines represent solid tumour types for which new drugs are urgently needed. The potencies of all of the Ti (IV) derivatives varied greatly (range from 10.8 μM - >1000 μM), although some trends were observed. In general, the dicationic analogues exhibited greater potency than the corresponding monocationic derivatives. -
Synthesis and Reactions of Ferrocene
R Carbon Synthesis and Reactions of Ferrocene R Carbon Carbon Contents Objectives 1 Introduction 1 Preparation of ferrocene 2 Acetylation of ferrocene 7 Preparation of [Fe(η-C5H5)(η-C6H6)]PF6 10 Reaction of [Fe(η-C5H5)(η-C6H6)] PF6 with nucleophiles 12 Manuscript prepared by Dr. Almas I. Zayya, Dr. A. Jonathan Singh and Prof. John L. Spencer. School of Chemical and Physical Sciences, Victoria University of Wellington, New Zealand. R Carbon Objectives Introduction The principal aims of these experiments are to The archetypal organometallic compound provide experience in the synthesis, isolation, ferrocene, [Fe(η-C5H5)2], is of historical importance purification and characterisation of organometallic since its discovery and structural characterisation compounds. Purification techniques include in the early 1950s sparked extensive research into distillation, sublimation, chromatography and the chemistry of metal sandwich compounds.1 crystallisation. The main characterisation Two of the chemists who first proposed the correct technique used in these experiments is 1H NMR structure of ferrocene (Figure 1), Geoffrey Wilkinson spectroscopy using the benchtop Spinsolve and Ernst Otto Fischer, were awarded the Nobel spectrometer. Furthermore, students will Prize in Chemistry in 1973 for their pioneering work also develop their synthetic skills using inert on the chemistry of sandwich complexes. atmosphere techniques. Ferrocene is an example of a π-complex in which interactions between the d-orbitals of the Fe2+ metal centre with the π-orbitals of the two planar - cyclopentadienyl ligands (C5H5 ) form the metal-ligand bonds. Thus, all the carbon atoms in the cyclopentadienyl rings are bonded equally to the central Fe2+ ion. Ferrocene exhibits aromatic properties and is thermally very stable. -
United States Patent Office Patented May 7, 1963
3,088,959 United States Patent Office Patented May 7, 1963 1. 2 or grouping of carbon atoms which is present in cyclo 3,088,959 pentadiene. This grouping is illustrated as PROCESS OF MAKENG CYCLOPENTADEENY NECKEL, NTROSYL COMPOUNDS Robert D. Feltham, Joseph F. Anzenberger, azad Jonatian T. Carrie, Pittsburgh, Pa., assignors to The Interaa tional Nickel Company, Inc., New York, N.Y., a corpo ration of Delaware No Drawing. FiRed Sept. 1, 1960, Ser. No. 53,374 The substituent groups on the cyclopentadiene moiety 6 Clains. (C. 260-439) 0. indicated as R, R2, R3, R and R5 are any one or more The present invention relates to the production of of hydrogen atoms, halogen atoms and/or organic groups nickel compounds and, more particularly, to the produc such as aliphatic groups, aromatic groups, alicyclic groups, tion of nickel nitrosyl compounds containing a group etc. The substituent groups can also bond at two posi having the cyclopentadienyl moiety. tions. Where this occurs, groups can substitute for adja Compounds such as cyclopentadienylnickel nitrosyl, 5 cent R groups, e.g., Ra and R3 and/or R4 and R5 to form methylcyclopentadienylnickel nitrosyl and other complex indene and other condensed ring structures. nitrosyl compounds containing a cyclopentadienyl-type As mentioned hereinbefore, when carrying out the proc group have been made. Such compounds have use as ess of the present invention, the reactants are reacted in gasoline additives. When such use is contemplated, it is the presence of a base. The base can advantageously be economically imperative that the compounds be produced 20 a nitrogen base or a phosphorus base or an alkoxide of a in good yield from the most readily available and inex metal having a strong hydroxide. -
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) --------------------------- -
United States Patent Office Patented Apr
2,882,288 United States Patent Office Patented Apr. 14, 1959 1 2 ber and character of substituents on the cyclopentadienyl carbon ring may otherwise be varied at will. Suitable 2,882,288 organic compounds include hydrocarbon compounds hav ORGANOVANADIUM HALIDES AND PROCESS ing the requisite alicyclic cyclopentadienyl carbon ring. OF PREPARATION Examples of such hydrocarbon compounds are cyclo John C. Brantley and Edward L. Morehouse, Snyder, pentadiene, its aliphatic derivatives as for example methyl, N.Y., assignors to Union Carbide Corporation, a cor ethyl, allyl and vinyl cyclopentadiene, its aromatic deriv poration of New York atives as for example phenyl cyclopentadiene, indene and its comparable derivatives. No Drawing. Application September 23, 1953 10 The formation of a dihalide according to this invention Serial No. 381,968 may be illustrated by the reaction between cyclopenta 11 Claims. (C. 260-429) dienyl magnesium chloride and VCla. The Grignard re agent may be prepared by reacting magnesium turnings with a lower alkyl chloride in a solvent, ethyl ether, bein This invention relates to organo-metallic compounds zene or the like for example, and reacting the resulting containing vanadium as the metal component. The in solution with cyclopentadiene. The cyclopentadienyl vention includes correlated improvements and discoveries magnesium chloride thus formed is then reacted with whereby such vanadium compounds having distinctive VCl4 in a suitable liquid medium and the organo properties are obtained. vanadium dichloride (C5H5)VCl may be recovered An object of the invention is to provide organo-metallic 20 from the reaction mixture. The same compound results compounds containing vanadium as the metallic compo from reaction of cyclopentadienyl magnesium chloride nent linked to the organic component by carbon to metal with VOCl3. -
1,3-Cyclopentadiene 2523
1,3-CYCLOPENTADIENE 2523 C5H6 MW: 66.10 CAS: 542-92-7 RTECS: GY1000000 METHOD: 2523, Issue 2 EVALUATION: FULL Issue 1: 15 May 1985 Issue 2: 15 August 1994 OSHA : 75 ppm PROPERTIES: liquid; d 0.8021 g/mL @ 20 °C; NIOSH: 75 ppm BP 42 °C; MP •85 °C; dimerizes to solid ACGIH: TWA 75 ppm (MP 32.5 °C); VP not available (1 ppm = 2.70 mg/m 3 @ NTP) SYNONYMS: none SAMPLING MEASUREMENT SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FID (maleic anhydride on Chromosorb 104, 100 mg/50 mg) ANALYTE: 1,3-cyclopentadiene-maleic anhydride adduct (see REAGENTS, 1.) FLOW RATE: 0.01 to 0.05 L/min DISSOLUTION: 10 mL ethyl acetate; stand 15 min VOL-MIN: 1 L @ 75 ppm -MAX: 5 L INJECTION VOLUME: 5 µL SHIPMENT: routine TEMPERATURE-INJECTION: 200 °C -DETECTOR: 250 °C SAMPLE -COLUMN: 155 °C STABILITY: at least 1 week @ 25 °C [1] CARRIER GAS: N2, 30 mL/min BLANKS: 2 to 10 field blanks per set COLUMN: 3 m x 3-mm OD stainless steel packed with 5% OV-17 on 100/120 mesh Chromosorb WHP ACCURACY CALIBRATION: analyte in ethyl acetate RANGE STUDIED: 73 to 370 mg/m 3 [1] (3-L samples) RANGE: 0.2 to 1.2 mg 1,3-cyclopentadiene per sample BIAS: 3.6% ˆ OVERALL PRECISION (S rT): 0.066 [2] ESTIMATED LOD: 0.01 mg per sample [1] ACCURACY: ± 16.5% PRECISION (S r): 0.031 @ 0.3 to 1.2 mg per sample [1] APPLICABILITY: The working range is 25 to 150 ppm (67 to 400 mg/m 3) for a 3-L air sample, based on sampler capacity at high relative humidity. -
Rhodium(Iii), and Iridium(Iii)
Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1980 Cyclometallated Compounds of Palladium(ii), Rhodium(iii), and Iridium(iii). Michael Anthony Gutierrez Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Gutierrez, Michael Anthony, "Cyclometallated Compounds of Palladium(ii), Rhodium(iii), and Iridium(iii)." (1980). LSU Historical Dissertations and Theses. 3562. https://digitalcommons.lsu.edu/gradschool_disstheses/3562 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This was produced from a copy of a document sent to us for microfilming. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help you understand markings or notations which may appear on this reproduction. 1. The sign or “ target” for pages apparently lacking from the document photographed is “Missing Page(s)”. If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure you of complete continuity. 2. When an image on the film is obliterated with a round black mark it is an indication that the film inspector noticed either blurred copy because of movement during exposure, or duplicate copy. -
A (Most Stable) > B > C > D
CHEMISTRY 314-81 MIDTERM # 2 – ANSWER KEY July 10, 2002 Statistics: · Average: 47 pts (67%); · Highest: 69 pts (99%); Lowest: 26 pts (37%) · Number of students performing at or above average: 12 (46%) 1. (7 pts) Mark as true (T) or false (F) the following statements. Do not explain! · (T) The Diels-Alder reaction is a [4+2] cycloaddition process; · (T) Molecular orbitals with equal number of nodes are degenerate; · (T) Molecular orbitals with equal energies are degenerate; · (F) The Diels-Alder reaction occurs faster with electron-deficient dienes; · (F) Cyclooctatetraene is an antiaromatic molecule; · (F) Ethylene is aromatic since it has 2 p-electrons; · (T) A molecule is UV-active if it has a conjugated system; 2. Circle all that apply: A. (2 pts) We say that benzene is stabilized because: a. It has higher than expected heat of hydrogenation; b. It has lower reactivity; c. It has low boiling point; d. It has large resonance energy; B. (2 pts) According to Hückel’s Rule a system is antiaromatic if: a. It is not conjugated; b. It is not planar; c. It has 4n p-electrons; d. It is not cyclic; C. (2 pts) Conjugated Dienes: a. Are more stable than the corresponding dienes with isolated double bonds; b. Are less stable than the corresponding dienes with cumulated double bonds; c. Are UV-active; d. Give predominantly 1,2-addition products at low temperatures ; D. (2 pts) The Diels-Alder reaction: a. Is stereospecific ; b. Is regiospecific ; c. Requires an s-cis conformation of the dienophile; d. Requires an s-trans conformation of the diene; 3. -
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https://theses.gla.ac.uk/ Theses Digitisation: https://www.gla.ac.uk/myglasgow/research/enlighten/theses/digitisation/ This is a digitised version of the original print thesis. Copyright and moral rights for this work are retained by the author A copy can be downloaded for personal non-commercial research or study, without prior permission or charge This work cannot be reproduced or quoted extensively from without first obtaining permission in writing from the author The content must not be changed in any way or sold commercially in any format or medium without the formal permission of the author When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given Enlighten: Theses https://theses.gla.ac.uk/ [email protected] ORGANOMSTALLIG DERIVATIVES OF TITANIUM A thesis presented for the Degree of Master of Science in the University of Glasgow by Chandubhai Chunibhai Patel Chemistry Department, The Royal College of Science and Technology, Glasgow* September, 1965* ProQuest Number: 10984228 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10984228 Published by ProQuest LLC(2018). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. -
Principles of Chemical Reactivity on the Diels-Alder Reaction in Ionic
Duquesne University Duquesne Scholarship Collection Electronic Theses and Dissertations Spring 1-1-2003 Principles of Chemical Reactivity on the Diels- Alder Reaction in Ionic Liquids and Lewis Acid Catalysis using Large-Scale Computations Orlando Acevedo Follow this and additional works at: https://dsc.duq.edu/etd Recommended Citation Acevedo, O. (2003). Principles of Chemical Reactivity on the Diels-Alder Reaction in Ionic Liquids and Lewis Acid Catalysis using Large-Scale Computations (Doctoral dissertation, Duquesne University). Retrieved from https://dsc.duq.edu/etd/7 This Worldwide Access is brought to you for free and open access by Duquesne Scholarship Collection. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Duquesne Scholarship Collection. For more information, please contact [email protected]. Principles of Chemical Reactivity on the Diels-Alder Reaction in Ionic Liquids and Lewis Acid Catalysis using Large-Scale Computations A Dissertation Presented to the Bayer School of Natural and Environmental Sciences Duquesne University In partial fulfillment of the requirements for the degree of Doctor of Philosophy by Orlando Acevedo May 2003 Name Orlando Acevedo Dissertation Title Principles of Chemical Reactivity on the Diels-Alder Reaction in Ionic Liquids and Lewis Acid Catalysis using Large-Scale Computations Degree Doctor of Philosophy Date May 3, 2003 APPROVED ___________________________________________ Dr. Jeffrey D. Evanseck Dissertation Director Associate Professor of Chemistry and Biochemistry APPROVED ___________________________________________ Dr. Jeffry D. Madura Chairman, Dept. of Chemistry and Biochemistry Associate Professor of Chemistry and Biochemistry APPROVED ___________________________________________ Dr. Bruce Beaver Associate Professor of Chemistry and Biochemistry APPROVED ___________________________________________ Dr. Daniel A. Singleton Professor of Chemistry, Texas A&M University APPROVED ___________________________________________ Dr. -
Probing the Strongest Aromatic Cyclopentadiene Ring By
Article Cite This: Organometallics 2018, 37, 3219−3224 pubs.acs.org/Organometallics Probing the Strongest Aromatic Cyclopentadiene Ring by Hyperconjugation Qiong Xie, Tingting Sun, and Jun Zhu* State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People’s Republic of China *S Supporting Information ABSTRACT: Hyperconjugation, an interaction of electrons in a σ orbital or lone pair with an adjacent π or even σ antibonding orbital, can have a strong effect on aromaticity. However, most work on hyperconjugative aromaticity has been limited to main-group substituents. Here, we report a thorough density functional theory study to evaluate the aromaticity in various cyclopentadienes that contain both main-group and transition-metal substituents. Our calcula- tions reveal that the strongest aromatic cyclopentadiene ring can be achieved by the synergy of trans influence and hyperconjugation caused by transition-metal substituents. Our findings highlight the great power of transition metals and trans influence in achieving hyperconjugative aromaticity, opening an avenue to the design of other novel aromatic organometallics. ■ INTRODUCTION nonatetraene derivatives.27 Ottosson and co-workers reported Aromaticity, one of the most important concepts in chemistry, that the variation in -
[Cp*Rh] Complexes Sup- Ported by a Hybrid Phosphine-Imine Ligand Julie A
Chemical and Electrochemical Properties of [Cp*Rh] Complexes Sup- ported by a Hybrid Phosphine-Imine Ligand Julie A. Hopkins, Davide Lionetti, Victor W. Day, and James D. Blakemore* Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, United States Supporting Information Placeholder ABSTRACT: A series of [Cp*Rh] complexes (Cp* = !5-pentamethylcyclopentadienyl) bearing the "2-[P,N]-8-(diphenylphosphino)quino- line (PQN) ligand have been prepared and characterized. Chemical or electrochemical reduction of the rhodium(III) form generates an isolable rhodium(I) complex; this rhodium(I) complex reacts with a range of organic acids to yield a rhodium(III) hydride bearing [Cp*] in the !5 mode and [PQN] in the expected "2 mode. Solid state structures of these three compounds from X-ray diffraction studies reveal only small changes in the intraligand bond distances across the series, suggesting the redox events associated with interconversion of these compounds are primarily metal-centered. Cyclic voltammetry data show that the rhodium(III) chloride complex undergoes a two-electron reduction at –1.19 V vs. ferrocenium/ferrocene, whereas the analogous solvento rhodium(III) acetonitrile complex undergoes two, sequential one-electron re- ductions. The rhodium(III) hydride undergoes an irreversible, ligand-centered reduction near –1.75 V vs. ferrocenium/ferrocene. Carrying out this reduction alone or in the presence of added of triethylammonium as a source of protons results in only modest yields of H2, as shown by bulk electrolyses and chemical reduction experiments. These results are discussed in the context of recent work with [Cp*Rh] complexes bearing more symmetric 2,2´-bipyridyl and diphosphine ligands.