DOCSLIB.ORG

Gold Chemistry with Ferrocene Derivatives As Ligands

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Gold Chemistry with Ferrocene Derivatives As Ligands Gold Chemistry with Ferrocene Derivatives as Ligands M ConcepciOn Gimeno and Antonio Laguna Universidad de Zaragoza-CSIC Departamento de Qufmica lnorganica-ICMA E 50009, Zaragoza, Spain Received: 26 February 1999 The synthesis and properties of gold complexes with l,l'-bis(diphenylphosphino)ferrocene (dppf), its sulfide (dppfS2) and disubstituted dithiocarbamate or thiolate ferrocene derivatives as ligands are reviewed. The ability of these metalloligands to modify their steric bite in order to adapt to different geometric requirements of the metal centres has allowed the synthesis of several gold complexes with unusual geometries and novel structures. The potential of the new compounds for a number of applications is considered. Organometallic ligands provide a convenient route to the first derivatives of this type to be reported (5, 6). By synthesis of heterometallic complexes. Amongst these reaction of the corresponding organa lithium ligands ferrocene derivatives have been the most widely derivatives with [AuPPh3]+ precursors the mono- and studied. Due to the high stability of ferrocenes and the di-aurated complexes, [(CsHS) Fe(CsH4AuPPh3)] and well-established methods for their incorporation into [Fe(CsH4AuPPh3) 2]' could be obtained (7). These more complex structures, they have become versatile complexes can incorporate additional [AuPPh3]+ building blocks for the synthesis of compounds with fragments, to give [(CsHs)Fe(CsH4)(AuPPh3h]+ or tailor-made properties (1-4). Ferrocene-containing [Fe{(CsH4)(AuPPh3hh]2+ (6, 7) as is shown in complexes are currently receiving much attention Equation 1: associated with their widespread utility, eg in organic synthesis, production of fine chemicals, homogeneous ©r-AUPPh3 catalysis, and materials chemistry. Fe Numerous derivatives have been reported in which the Ph3PA~ cyclopentadienyl rings of ferrocene carry organic groups with one or more donor atoms. An important feature of these potential ligands is their flexibility: the bidentate The bonding situation in the latter complexes has representatives can adapt as chelating groups to different been described in terms of 3-centre-2-electron bonding, geometric requirements of a given metal centre and act as but resonance structures in which the aromaticity of the bridging ligands. Some of the complexes obtained with ring is lost and the positive charge delocalized over the these ligands have interesting redox properties and unusual ring are also acceptable. The short Au···Au distances structures (1-4). The coordination of ferrocene and of (2.77 A) and narrow Au-C-Au angles (78°) are indicative mono- or di- substituted diphenylphosphino, dipheny­ of a strong interaction between the gold centres. lthiophosphoryl, dithiocarbamate and thiolate derivatives to gold(I) and gold(III) leads to interesting three- or four­ coordinate mono- and polynuclear gold complexes. COMPLEXES WITH P-SUBSTITUTED FERROCENE LIGANDS FERROCENYL COMPLEXES The diphosphine 1,1 'bis (diphenylphosphino) ferrocene Ferrocenylgold compounds with the gold centre (dppf) has received a great deal of attention due to its directly attached to the cyclopentadienyl rings were the chemical uniqueness and industrial importance (1). It 90 C6\9' Gold Bulletin 1999, 32 (3) can act as a bridging or chelating ligand in two-, three-, they show no superior properties to those for and four-coordinated gold(1) and gold (III) compounds evaluated previously (10). compounds. Displacement of tetrahydrothiophene The reaction of dppf with [AuCI(SR2) lleads to the (tht) in gold(1) complexes such as [AuX(tht) 1 (X=CI, formation of the chloro complexes [(dppf)(AuClhl (1, C6FS), [Au(tht)LlCI04 (L=phosphine, ylide) or X=Cl) , [AuCI(dppf)l and [AuCI(dppfhL depending [Au(ththlCI04 by the diphosphine leads to neutral on the molar ratio used (8, 9, 12, 13). The 197Au and representatives [(dppf)(AuXhl (1) (Box 1), to cationic S7Fe Mbssbauer and 31 P NMR spectroscopic data of dinuclear complexes [(dppf)(AuLh](CI04h and to the products indicate the existence of two different three- and four-coordinate mononuclear derivatives gold (I) coordination geometries in the solid state: [(dppf)AuPR3lCl04 (2) and [Au(dppf)2lCl04 (8a) linear and trigonal (11). The dinuclear respectively. The crystal structure of [(dppf)(AuClhl has only marginal activity against the [(dppf)AuPPh3lCl04 indicates a trigonal-planar Au P388 leukaemia mouse model (12) . The crystal coordination. The Au-P distances (2.343 - 2.409 A) structure of one of its known modifications shows a are shorter than the Ag-P ones (2.424 - 2.480 A) in the nearly linear P-Au-CI unit and intermolecular gold­ analogous [(dppf)AgPPh3lCI04 (8b), in agreement gold contacts of 3.083(1) A (12), whereas no Au .. ·Au with theoretical predictions (8c). [Au(dppf) 2l CI04 interactions have been found in other modifications of undergoes a dimerization process with liberation of the same compound (14) . The reaction of one dppf and formation of [(dppf)Au(r­ [(dppf)(AuCI) 2l with dppf (1: 1 molar ratio) gives dppf) AU(dppf) ](CI04) 2 (3) which contains bridging [AuCI(dppf) 1 as an intermediate, which readily and chelating diphosphines (8b). The same dication is polymerizes to give a chain polymer based on trigonal present in [(dppf)Au(r-dppf)Au(dppf)](N03)2, CIAuP2 units (4) (9, 13). obtained by the reaction of dinuclear [(dppf)(AuCI) 2l From [(dppf)(AuCl) 2l other dinuclear complexes with AgN03 and NaHC03 (9). Cyclic voltammetry of [(dppf)(AuXhl (X Br, 1, 2-pyridinethiolate some of these compounds reveals one chemically (Spy) or S2CNR2) can be obtained (14). reversible phosphinoferrocene-based oxidation (9). The complex [(dppf)(AuSpYhl with its nitrogen donor atom can coordinate to [AuPPh2Mel+ units to give the polynuclear compounds Box 1 [(dppf){AuSpy(AuPPh2Me)hl (OTfh (OTf = CF3S03) ~Ph2 -Q.r-P-AuX and [(dppf){AuSpy(AuPPh2Mehh](OTf)4. The latter decomposes in solution and the trinuclear complex Ph 2 Fe XAU-~ [AU3(r-dppf)(r3_Spy)(PPh2Me)](OTf)2 (5) (Box 2) is obtained, which represents the first example where a (1) pyridinethiolate ligand bridges three gold centres. The gold atoms have geometries slightly distorted from <@rP-AUPhl P].. .. linearity, probably due to the weak gold-gold CI" Ph2 Fe . '. PPh Alr ..[ .. ~ 2 interactions (3.0985(12) and 3.2105(13) (A) (14). Ph (' n 2 The reaction of [(dppf)(AuClhl with an excess of (4) LiR in diethyl ether affords the organa gold (I) -dppf complexes [(dppf)(AuR) 2l [R = Me, Ph, I-naphthyl, 9- anthryl, pyren-l-yl(CI6H g), C==CPh, C==CButl. Similar complexes, such as the dinuclear Their photophysical and electrochemical properties [(dppomf)(AuXhl (X = CI, C6FS) or the mononuclear have been studied (15). Excitation of these complexes at three-coordinate compounds [(dppomf)AuXl can be X. > 330 nm gives weak emissions in dichloromethane obtained using the related diphosphine 1, 1'­ solutions. The electrochemical data show a quasi­ bis(diphenylphosphino)octamethylferrocene (dppomf) reversible wave, due to the oxidation of the dppf, and (10) . The gold atom is trigonal planar in an irreversible one assigned to Au (I) - Au (II) [(dppomf)AuCll. Electrochemical studies (10) show oxidation. The structure of [(dppf){Au(CI6Hg)hl is the formation of Fe (III) derivatives of the similar to that of the chIaro derivative. The metallophosphine gold(1) complexes, which can also be heterometallic complexes [(dppf)(Au{M(CO) s}hl obtained by direct reaction of the precursors with (M = Mn, Re (6)) are obtained by the reaction of electrochemically generated [FeCp2l+. The cytotoxic [(dppf)(AuClhl with Na[M(CO)Sl (16). However, properties of these complexes have been studied, but reaction with K2[Pd(CN)4l results in ligand ~ GoldBulletin 1999,32(3) 91 displacement with formation of [(dppf){Au(CN)12] Box 3 instead of metal-metal bond formation. The X-ray p.p = dppf; E = S or S e z photoelectron spectroscopic data for complex 6 suggest MePh "" l 2+ a polarization of the AuB+- ReB- bonds (16). The :~ complexes [M(CO)S(dppf)] (M = Cr, Mo, W) behave A~:;\ MePhzl""" AU""Au like a mono dentate phosphine ligand and react with rf \p [AuCl(SMe2)] to yield the heterometallic complex (8) '------"' [M(CO)S(r-dppf)AuCl] (17). Box 2 2+ <.9r~~UrFe : o ~ <g>-r-A'r Phz ". u MePh2P (5) (6) [(dppf){Au(C6F sh}] Cl04 have been obtained by displacement of tht in [AU(C6Fs)3tht] or [Au (C6FS) 2(thth] Cl04 by the dppfligand (8a). Treatment of [(dppf)(AuClh] with Li2S (molar The chiral aminoferrocenyldiphosphine ratio 1: 1) gives [S (AU2dPPf)] (7) (Box 3), in which the [Fe(C6H4PPh2){C6H3(PPh2)­ sulfur atom can further coordinate neutral or cationic (CHMeNMeCH2CH2NMe2)}] reacts with gold (I) fragments to give the trinuclear complexes [AuCl(SMe2)] to give the trinuclear derivative, [S{Au (C6F S)} (AU2dPPf)] and [S (AuL)(Au2dPPf)] Cl04 [{Fe(C6H4PPh2){C6H3(PPh2) (CHMeNMeCH2CH2NM (L = CH2PPh3, PPh3, PPh2Me), the tetranuclear e,u}12(AuClh] (11) (Box 4), which is an active catalyst for complexes [S(AuLh(Au2dPPf)](Cl04h (L = PPh3, the enantioselective coupling of isocyanoacetate esters with PPh2Me (8)), and the hexanuclear complex [(r­ aldehydes, to form dihydrooxazoles (Equation 2) (24): AU2dppf){S(Au2dppf)12](OTfh (9), in which two SAU3 units are linked by the dppf ligands (18). The 1\ ,cOOEt R COOEt coordination sphere of the sulfur atom in 8 can be RCHO + CNCH2COOEr - nN + HN regarded as a trigonal bipyramid with one of the apical 0-...,; 0-...,; (2) positions occupied by the lone pair of electrons and the other by the gold atoms. The complex is electron­ Diferrocenylphenylphosphine (PF C2Ph) [F c = deficient, however, since only three bonding molecular (CsHs)Fe(CsH4)] reacts with gold(1) derivatives to orbitals are occupied (19, 20). All these complexes afford the neutral or cationic complexes, display short gold-gold interactions. The reactions of [AuX(PFc2Ph)] (X=Cl, C6FS) and [Au(PFc2Ph) [S (AU2dPPf)] with the gold (III) precursors (PR3)]Cl04 (PR3 = PFC2Ph, PPh3) (25).
Load more

Recommended publications
  • Iron-Catalysed Transformation of Molecular Dinitrogen Into Silylamine Under Ambient Conditions
    ARTICLE Received 6 Sep 2012 | Accepted 6 Nov 2012 | Published 4 Dec 2012 DOI: 10.1038/ncomms2264 Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions Masahiro Yuki1, Hiromasa Tanaka2, Kouitsu Sasaki1, Yoshihiro Miyake1, Kazunari Yoshizawa2 & Yoshiaki Nishibayashi1 Although stoichiometric transformations using transition metal–N2 complexes have been well investigated towards the goal of nitrogen fixation under mild reaction conditions, only a few examples of the catalytic transformations of N2 using transition metal–N2 complexes as catalysts have been reported. In almost all the catalytic systems, the use of Mo is essential to realize the catalytic transformation of N2, where Mo–N2 complexes are considered to work as effective catalysts. Here we show the first successful example of the Fe-catalysed transfor- mation of N2 into N(SiMe3)3 under ambient conditions, in which iron complexes such as iron pentacarbonyl [Fe(CO)5] and ferrocenes have been found to work as effective catalysts. A plausible reaction pathway is proposed, where Fe(II)–N2 complex bearing two Me3Si groups as ancillary ligands has an important role as a key reactive intermediate, with the aid of density-functional-theory calculations. 1 Institute of Engineering Innovation, School of Engineering, University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan. 2 Institute for Materials Chemistry and Engineering, International Research Center for Molecular Systems, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan. Correspondence and requests for materials should be addressed to K.Y. (email: [email protected]) or to Y.N. (email: [email protected]).
    [Show full text]
  • Organometrallic Chemistry
    CHE 425: ORGANOMETALLIC CHEMISTRY SOURCE: OPEN ACCESS FROM INTERNET; Striver and Atkins Inorganic Chemistry Lecturer: Prof. O. G. Adeyemi ORGANOMETALLIC CHEMISTRY Definitions: Organometallic compounds are compounds that possess one or more metal-carbon bond. The bond must be “ionic or covalent, localized or delocalized between one or more carbon atoms of an organic group or molecule and a transition, lanthanide, actinide, or main group metal atom.” Organometallic chemistry is often described as a bridge between organic and inorganic chemistry. Organometallic compounds are very important in the chemical industry, as a number of them are used as industrial catalysts and as a route to synthesizing drugs that would not have been possible using purely organic synthetic routes. Coordinative unsaturation is a term used to describe a complex that has one or more open coordination sites where another ligand can be accommodated. Coordinative unsaturation is a very important concept in organotrasition metal chemistry. Hapticity of a ligand is the number of atoms that are directly bonded to the metal centre. Hapticity is denoted with a Greek letter η (eta) and the number of bonds a ligand has with a metal centre is indicated as a superscript, thus η1, η2, η3, ηn for hapticity 1, 2, 3, and n respectively. Bridging ligands are normally preceded by μ, with a subscript to indicate the number of metal centres it bridges, e.g. μ2–CO for a CO that bridges two metal centres. Ambidentate ligands are polydentate ligands that can coordinate to the metal centre through one or more atoms. – – – For example CN can coordinate via C or N; SCN via S or N; NO2 via N or N.
    [Show full text]
  • 18- Electron Rule. 18 Electron Rule Cont’D Recall That for MAIN GROUP Elements the Octet Rule Is Used to Predict the Formulae of Covalent Compounds
    18- Electron Rule. 18 Electron Rule cont’d Recall that for MAIN GROUP elements the octet rule is used to predict the formulae of covalent compounds. Example 1. This rule assumes that the central atom in a compound will make bonds such Oxidation state of Co? [Co(NH ) ]+3 that the total number of electrons around the central atom is 8. THIS IS THE 3 6 Electron configuration of Co? MAXIMUM CAPACITY OF THE s and p orbitals. Electrons from Ligands? Electrons from Co? This rule is only valid for Total electrons? Period 2 nonmetallic elements. Example 2. Oxidation state of Fe? The 18-electron Rule is based on a similar concept. Electron configuration of Fe? [Fe(CO) ] The central TM can accommodate electrons in the s, p, and d orbitals. 5 Electrons from Ligands? Electrons from Fe? s (2) , p (6) , and d (10) = maximum of 18 Total electrons? This means that a TM can add electrons from Lewis Bases (or ligands) in What can the EAN rule tell us about [Fe(CO)5]? addition to its valence electrons to a total of 18. It can’t occur…… 20-electron complex. This is also known Effective Atomic Number (EAN) Rule Note that it only applies to metals with low oxidation states. 1 2 Sandwich Compounds Obeying EAN EAN Summary 1. Works well only for d-block metals. It does not apply to f-block Let’s draw some structures and see some new ligands. metals. 2. Works best for compounds with TMs of low ox. state. Each of these ligands is π-bonded above and below the metal center.
    [Show full text]
  • 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.
    [Show full text]
  • Oxidation of Ferrocene Derivatives with Dibenzoyl Peroxide and Meta-Chloroperoxybenzoic Acid
    Cleveland State University EngagedScholarship@CSU ETD Archive 2018 Oxidation of Ferrocene Derivatives with Dibenzoyl Peroxide and Meta-Chloroperoxybenzoic Acid Jos M. Halstead Cleveland State University Follow this and additional works at: https://engagedscholarship.csuohio.edu/etdarchive Part of the Chemistry Commons, and the Medicine and Health Sciences Commons How does access to this work benefit ou?y Let us know! Recommended Citation Halstead, Jos M., "Oxidation of Ferrocene Derivatives with Dibenzoyl Peroxide and Meta- Chloroperoxybenzoic Acid" (2018). ETD Archive. 1108. https://engagedscholarship.csuohio.edu/etdarchive/1108 This Dissertation is brought to you for free and open access by EngagedScholarship@CSU. It has been accepted for inclusion in ETD Archive by an authorized administrator of EngagedScholarship@CSU. For more information, please contact [email protected]. OXIDATION OF FERROCENE DERIVATIVES WITH DIBENZOYL PEROXIDE AND META-CHLOROPEROXYBENZOIC ACID JOSHUA M. HALSTEAD Bachelor of Science in Chemistry Cleveland State University May 2011 Master of Science in Chemistry Cleveland State University May 2013 submitted in partial fulfillment of requirements for the degree DOCTOR OF PHILOSOPHY IN CLINICAL AND BIOANALYTICAL CHEMISTRY at the CLEVELAND STATE UNIVERSITY DECEMBER 2018 DEDICATION This work is dedicated to Dr. John Masnovi, who sadly passed away shortly before its completion. I will remember him for his insightful instruction, kind demeanor, and willingness to help anyone learn. He will be missed. We hereby approve this dissertation for Joshua M. Halstead Candidate for the Doctor of Philosophy in Clinical-Bioanalytical Chemistry degree for The Department of Chemistry and the CLEVELAND STATE UNIVERSITY’S College of Graduate Studies by _________________________________________________________________ Dissertation Chairperson, Dr.
    [Show full text]
  • Experiment #4 the Preparation of Ferrocene & Acetylferrocenes1
    Experiment #4: The Preparation of Ferrocene & Acetylferrocene MASSACHUSETTS INSTITUTE OF TECHNOLOGY Department of Chemistry 5.311 Introductory Chemical Experimentation EXPERIMENT #4 THE PREPARATION OF FERROCENE & ACETYLFERROCENES1 I. Purpose The principal aims of this experiment are to provide background information about and experience in: S the synthesis and electronic structure of ferrocene (1), ( -C5H5)2Fe [bis(pentahaptocyclopentadienyl) iron]2 S the synthesis of an ionic liquid, as environment for the acetylation of ferrocene S the use of inert atmospheres (including glove box techniques) S recrystallization or sublimation S the use of GC/MS and thin-layer chromatography as analytical tools and column chromatography as a purification technique • the concepts of Green Chemistry such as Atom Economy3 and alternative non-polluting solvents Ferrocene is a historically important molecule. The initial recognition of the structure of 4 C10H10Fe in 1951 spawned a vast area of chemistry, viz., transition metal organometallic chemistry. This field is still developing and has produced a huge number of compounds in which saturated, unsaturated, and aromatic organic fragments are bonded directly to metals. All carbon atoms in the two cyclopentadienyl rings are equally bonded to the central ion by electrons in the rings. The sandwich structure proposed by Wilkinson and Fischer5,6 (Nobel prize in 1973) in early 1 Mircea D. Gheorghiu designed the experiment to include the acetylation of ferrocene in ionic liquid. 2 The word hapto means in Greek to fasten. Pentahapto therefore, is to be taken as “fastened in five places.” The greek letter followed by a superscript indicates how many atoms of the ligand are attached to the metal.
    [Show full text]
  • Ferrocene Functionalized Single-Walled Carbon Nanotube Bundles
    1200 J. Phys. Chem. C 2007, 111, 1200-1206 Ferrocene Functionalized Single-Walled Carbon Nanotube Bundles. Hybrid Interdigitated Construction Film for L-Glutamate Detection Xing-Jiu Huang,*,† Hyung-Soon Im,† Do-Hoon Lee,‡ Hak-Sung Kim,‡ and Yang-Kyu Choi*,† Nano-Bio-Electronic Lab, Department of Electrical Engineering and Computer Science and Department of Biological Sciences, Korea AdVanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, Daejeon, South Korea ReceiVed: September 4, 2006; In Final Form: NoVember 9, 2006 A ferrocene functionalized SWCNT noncovalent nanohybrid was investigated by using a ferrocene/SWCNT interdigitated construction film as an electrode for L-glutamate detection. Ferrocene could immobilize on the surface of SWCNT bundles, and the ferrocene/SWCNT hybrid had a high stability not only in water but also in an organic solvent such as ethanol and acetone (no sediment was observed for more than 3 months). The nanohybrid could not only be thoroughly dispersed in ethanol but also adhere tightly onto glass substrates to form an interdigitated construction film. Owing to the existence of more carbon nanotubes, more active electrochemical mediators, and the unique interdigitated structure of the film, the ferrocene/SWCNT electrode exhibited a high catalytic efficiency, high sensitivity, and fast response during the detection of a low concentration of L-glutamate (1 µM). A good linear relationship between current and concentration was obtained from1to7µM. 1. Introduction of AST and ALT in monitoring patients with liver diseases. AST and ALT are also biological catalysts, and the assay of all Carbon nanotubes are an attractive material for applications AST and ALT activity is based on the following enzyme 1,2 in electronic or sensor devices.
    [Show full text]
  • Renewable Fuels
    research highlights nucleobase and the phosphate linker — to have proposed a chemical method that produce nucleic acid analogues with very could be used to upgrade more common and different properties. Metal-containing higher-yielding fermentation products into a variants have also been made, in which the mixture containing the desired hydrocarbons. two strands of the double helix are held together by metal–ligand coordination rather O O than hydrogen bonding. Now, James Tucker and co-workers 1.7 % 49.8 % at the University of Birmingham, UK, Eye of the beholder have taken the first steps towards making O O From pesky biochemists winning the a DNA mimic in which metals form an Nobel Prize in Chemistry, to the social integral part of the polymer backbone. < 0.5 %8.3 % construction of scientific ideas. Is it all On recognizing that the distance between just a matter of perspective? the two cyclopentadienyl (Cp) rings in O O ferrocene is very similar to the distance Considering the time of year, it would between adjacent sets of stacked base pairs be rude not to mention this year’s Nobel in B-DNA, the team set about designing and 4.2 % 2.8 % Laureates in Chemistry, Robert J. Lefkowitz making a nucleic acid analogue based on and Brian K. Kobilka. Being awarded the this well-known organometallic compound. Clostridium acetobutylicum is a bacterium prize “for studies of G-protein-coupled The resulting ferrocene nucleic acid that has been known for almost 100 years, receptors” resulted in a tedious furore (FcNA) structure is made up of a repeating and it produces, by fermentation, a mixture of owing to the awarding of the prize to C3-linker–ferrocene–C3-linker–phosphate acetone, butanol and ethanol (widely known biochemists.
    [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]
  • And Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks
    Materials 2015, 8, 3767-3775; doi:10.3390/ma8063767 OPEN ACCESS materials ISSN 1996-1944 www.mdpi.com/journal/materials Article Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks Wencai Zhou, Christof Wöll and Lars Heinke * Institut für Funktionelle Grenzflächen (IFG), Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany; E-Mails: [email protected] (W.Z.); [email protected] (C.W.) * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +49-721-608-2-2319; Fax: +49-721-608-2-3478. Academic Editor: Sergey Vasenkov Received: 5 May 2015 / Accepted: 9 June 2015 / Published: 19 June 2015 Abstract: The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs), is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM), the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1), whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane. Keywords: metal-organic frameworks; diffusion; mass transfer; gas phase; liquid phase 1. Introduction Metal-organic frameworks (MOFs) are crystalline, nanoporous hybrid materials, which attract a considerable amount of attention due to their unique properties, such as their very large specific surface area and their enormous variety [1,2].
    [Show full text]
  • 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.
    [Show full text]
  • Cytotoxicity of Ferrocenyl–Ethynyl Phosphine Metal Complexes of Gold and Platinum
    ANTICANCER RESEARCH 31: 825-830 (2011) Cytotoxicity of Ferrocenyl–Ethynyl Phosphine Metal Complexes of Gold and Platinum ELEANOR FOURIE1, ELIZABETH ERASMUS1, JANNIE C. SWARTS1, ALEXANDER JAKOB2, HEINRICH LANG2, GISELA K. JOONE3 and CONSTANCE E.J. VAN RENSBURG3 1Department of Chemistry, University of the Free State, Bloemfontein, 9300, Republic of South Africa; 2Institut für Chemie, Technishe Universität Chemnitz, 09111 Chemnitz, Germany; 3Department of Immunology, Institute for Pathology, University of Pretoria, Pretoria, 0001, Republic of South Africa Abstract. Background: Ferrocene derivatives may possess Cl– ion has on the cytotoxicity of these neutral gold ≡ antineoplastic activity. Those with low ferrocenyl reduction complexes. The platinum complex [(Fc-C C-PPh2)2PtCl2], potentials often have the highest anticancer activity, as cell compound 5, resembling the structure of cisplatin, in components have to oxidise them to the active ferrocenium principle should exhibit good cytotoxicity, but was not tested species before cytotoxicity can be recorded. Some gold(I) due to its total insolubility in any biocompatible medium. complexes also possess anticancer activity. This study examined the cytotoxicity of ferrocenyl-ethynyl and Potentially good chemotherapeutic drugs frequently find ruthenocenyl-ethynyl complexes of gold and platinum. The limited clinical use due to the many negative medical and results were related to the ease of iron oxidation in the physical side-effects they exhibit. For cisplatin, [(H3N)2PtCl2], ferrocenyl fragment
    [Show full text]