Functionalized Organogold(I) Complexes From
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FULL PAPER (CF3)3Au As a Highly Acidic Organogold(III) Fragment
FULL PAPER (CF3)3Au as a Highly Acidic Organogold(III) Fragment Alberto Pérez-Bitrián,[a] Miguel Baya,[a] José M. Casas,[a] Larry R. Falvello,[b] Antonio Martín,[a] and Babil Menjón*[a] Dedicated to Professor Juan Forniés on the occasion of his 70th birthday Abstract: The Lewis acidity of perfluorinated trimethylgold, (CF3)3Au, was soon realized that fluorination of the organic group R has been assessed by theoretical and experimental methods. It has resulted in enhancement of the Lewis acidity in the F [9–11] been found that the (CF3)3Au unit is much more acidic than its non- corresponding R 3B derivatives. In fact, the most widely fluorinated homologue (CH3)3Au, probably setting the upper limit in used borane is by far (C6F5)3B, which exhibits a considerable [12] the acidity scale for any neutral R3Au organogold(III) species. The Lewis acidity. The perfluoromethyl-derivative (CF3)3B would significant acidity increase upon fluorination is in line with the CF3 be expected to exhibit even stronger Lewis acidity. Although this group being in fact more electron-widthdrawing than CH3. The compound has not yet been isolated as such, its derivatives [13] solvate (CF3)3Au·OEt2 (1) is presented as a convenient synthon of (CF3)3B·L and, especially the singular carbonyl compound [14] the unsaturated, 14-electron species (CF3)3Au. Thus, the weakly (CF3)3BCO, evidence a greatly enhanced acidity of the [15,16] coordinated ether molecule in 1 is readily replaced by a variety of (CF3)3B moiety. neutral ligands affording a wide range of (CF3)3AuL compounds, The trifluoromethyl group, CF3, exhibits properties departing which have been isolated and conveniently characterized. -
Cubane and Triptycene As Scaffolds in the Synthesis of Porphyrin Arrays
Cubane and Triptycene as Scaffolds in the Synthesis of Porphyrin Arrays Submitted by Gemma M. Locke B.A. (Mod.) Medicinal Chemistry Trinity College Dublin, Ireland A thesis submitted to the University of Dublin, Trinity College for the degree of Doctor of Philosophy Under the Supervision of Prof. Dr. Mathias O. Senge University of Dublin, Trinity College September 2020 Declaration I declare that this thesis has not been submitted as an exercise for a degree at this or any other university and it is entirely my own work. I agree to deposit this thesis in the University’s open access institutional repository or allow the Library to do so on my behalf, subject to Irish Copyright Legislation and Trinity College Library conditions of use and acknowledgement. I consent to the examiner retaining a copy of the thesis beyond the examining period, should they so wish. Furthermore, unpublished and/or published work of others, is duly acknowledged in the text wherever included. Signed: ____________________________________________ March 2020 Trinity College Dublin ii Summary The primary aim of this research was to synthesise multichromophoric arrays that are linked through rigid isolating units with the capacity to arrange the chromophores in a linear and fixed orientation. The electronically isolated multichromophoric systems could then ultimately be tested in electron transfer studies for their applicability as photosynthesis mimics. Initially, 1,4-diethynylcubane was employed as the rigid isolating scaffold and one to two porphyrins were reacted with it in order to obtain the coupled product(s). Pd-catalysed Sonogashira cross-coupling reactions were used to try and achieve these bisporphyrin complexes. -
Organogold Chemistry: I Structure and Synthesis
Organogold Chemistry: I Structure and Synthesis R V Parish Department a/Chemistry, UMIST, Manchester, M60 1QD, UK Organogold chemistry is enjoying a resurgence of interest as useful applications, largely physical or medicinal, are being found. There is also a wide range of novel molecules, some with curious structures. This article reviews the structures and syntheses of recently discovered gold compounds. A later article will describe their reactions and applications. Organogold derivatives have been known for almost example, reference 2), and deals with the preparation, 100 years. Many fascinating compounds and reactions structures, properties and applications of some of the have been discovered but, until recently, they have more interesting organogold systems; the examples found little practical application. However, the last ten given are drawn principally from those reported during to fifteen years have seen the development of new the last ten years (a more comprehensive treatment is materials with potential applications in non-linear found in reference 3). The intention is to exemplify optics, conjugated linear polymers (potential molecular rather than to be comprehensive, and no mention at all wires), liquid crystals, chemical vapour deposition and is made of cluster compounds. Complexes in which anti-tumour agents (see Box 1). On the other hand, in carbonyl, cyano, or isonitrile ligands provide the only marked contrast to the neighbouring noble metals, Au-C bonds are also ignored. For convenience, the compounds of gold have been very little used in review is divided into two parts: this part deals with homogeneous catalysis (but see reference 1). This the wide variety of organic ligands now available and review attempts to update previous treatments (see, for the structure and synthesis of the gold compounds derived from them; the second part treats the reactions and applications of these compounds. -
And 5,10,15,20-Tetraalkylporphyrins: Implications For
336 J. Am. Chem. SOC.1988, 110, 336-342 values being Ai,(IH) = 127.2 G and gs0= 2.0042. Since these intermediates produced under reactive laser sputtering21and other results are very similar to those calculated from the neon data, high-energy condition^.^' The use of the neon ESR matrix namely, Ais0(lH) = 128.6 G and giso= 2.0038, it is reasonable technique for studying ion products formed injon-neutral reactions to conclude that these parameters are characteristic of the un- has also been demonstrated for the following reactions which are complexed cation irrespective of the nature of the matrix. Con- important in stratospheric chemistry: CO + CO' -+ C202+,42 sequently, the significantly different parameters observed for the N2 + N2+- N4+,43N2 + CO+ - N2CO+,'and O2 + 02+- cation above 120 K in the CFC1, matrix (Table 111) now become 04+.44 anomalous for a dissociated cation. On the other hand, these 120 K parameters are just what would be expected if the complex Acknowledgment. The neon matrix ESR experiments were persists and the loss of fine structure results simply from a motional conducted at Furman University with support from the National averaging of the 35Cl hyperfine tensor components. Science Foundation (CHE-8508085), the General Electric Except for a recent investigation of the cubane radical cation Foundation, the Amoco Foundation, and Research Corporation. (C8H8+),39the acetaldehyde ion is the largest cation studied to A new ESR spectrometer was made possible by a chemistry date by the neon matrix ESR method. Given the high resolution equipment grant to Furman University from the Pew Memorial that can be achieved in neon and the chance of preferential Trust. -
LIST of PUBLICATIONS of JOSEF MICHL B: Book P: Patent C
LIST OF PUBLICATIONS OF JOSEF MICHL B: Book P: Patent C: Communication R: Review or Chapter in a Book P 1. Kopecký, J.; Michl, J. "Zpùsob výroby pyrrolo(2,3-d)-pyrimidinù", Czechoslovak patent no. 97821, August 11, 1959. C 2. Zuman, P.; Michl, J. "Role of Keto-Enol Tautomerism in the Polarographical Reduction of Some Carbonyl Compounds", Nature 1961, 192, 655. C 3. Horák, V.; Michl, J.; Zuman, P. "A Contribution to the Studies of Elimination Reactions of Mannich Bases, Using Polarographic Method", Tetrahedron Lett. 1961, 744. C 4. Zahradník, R.; Michl, J.; Koutecký, J. "Fluoranthene-like Hydrocarbons: MO-LCAO Study of Electronic Spectra, Charge-Transfer Spectra and Polarographic Reduction", J. Chem. Soc. 1963, 4998. 5. Koutecký, J.; Hochman, P.; Michl, J. "Calculation of Electronic Spectra of Non-Alternant Conjugated Hydrocarbons by the Semiempirical Method of Limited Configuration Interaction", J. Chem. Phys. 1964, 40, 2439. 6. Zahradník, R.; Michl, J.; Koutecký, J. "Tables of Quantum Chemical Data. II. Energy Characteristics of Some Non-Alternant Hydrocarbons", Collect. Czech. Chem. Commun. 1964, 29, 1932. 7. Zahradník, R.; Michl, J.; Koutecký, J. "Tables of Quantum Chemical Data. III. Molecular Orbitals of Some Fluoranthene-like Hydrocarbons, Cyclopentadienyl, and Some of its Benzo and Naphtho Derivatives", Collect. Czech. Chem. Commun. 1964, 29, 3184. 8. Zahradník, R.; Michl, J. "Electronic Structure of Non-Alternant Hydrocarbons, Their Analogues and Derivatives. Introductory Remarks", Collect. Czech. Chem. Commun. 1965, 30, 515. 9. Zahradník, R.; Michl, J. "Electronic Structure of Non-Alternant Hydrocarbons, Their Analogues and Derivatives. I. A Theoretical Treatment of Reid's Hydrocarbons", Collect. Czech. Chem. Commun. -
Structure and Bonding of New Boron and Carbon Superpolyhedra
Structural Chemistry (2019) 30:805–814 https://doi.org/10.1007/s11224-019-1279-5 ORIGINAL RESEARCH Structure and bonding of new boron and carbon superpolyhedra Olga A. Gapurenko1 & Ruslan M. Minyaev1 & Nikita S. Fedik2 & Vitaliy V. Koval1 & Alexander I. Boldyrev2 & Vladimir I. Minkin1 Received: 16 November 2018 /Accepted: 1 January 2019 /Published online: 10 January 2019 # Springer Science+Business Media, LLC, part of Springer Nature 2019 Abstract Using the DFT methods, we computationally predict the stability of cage compounds E4nRn (E = B, C; R = H, F; n = 4, 8, 12, 24) based on Platonic bodies and Archimedean polyhedrons in which all vertices are replaced by tetrahedral E4R fragments. Cage compounds B60R12 and C60 with pyramidal units B5RorC5 are also examined and it is shown that only boron compounds are stable. The nature of chemical bonding in the discussed compounds is analyzed using the AdNDP and NBO methods. The hydrocarbons have classical 2c-2e C-C σ-bonds, while the boron compounds are formed by the polyhedral units with the delocalized multicenter bonds which connected three and more boron atoms. The new example of spherical aromaticity accord- 2 ing to the 2(N+1) rule in the case of B16F4 with multicenter 16c-2e bonds are revealed. Stable compound B60H12 contains 12 5c- 2e B-B bonds. Keywords Сage clusters . Chemical bonding . 3c-2e bond . Spherical aromaticity . AdNDP . NBO Construction of novel allotropic forms of carbon based on was proposed [1] as the system with the same symmetry as the tetrahedrane- and cubane-like building blocks was pro- sp3-carbon to replace the carbon atoms in the diamond posed by Burdett and Lee [1] and by Johnston and lattice. -
Advanced Physical Techniques in Inorganic Chemistry: Probing Small Molecule Activation
Advanced Physical Techniques in Inorganic Chemistry: Probing Small Molecule Activation The Harvard community has made this article openly available. Please share how this access benefits you. Your story matters Citation Anderson, Bryce L. 2016. Advanced Physical Techniques in Inorganic Chemistry: Probing Small Molecule Activation. Doctoral dissertation, Harvard University, Graduate School of Arts & Sciences. Citable link http://nrs.harvard.edu/urn-3:HUL.InstRepos:33493292 Terms of Use This article was downloaded from Harvard University’s DASH repository, and is made available under the terms and conditions applicable to Other Posted Material, as set forth at http:// nrs.harvard.edu/urn-3:HUL.InstRepos:dash.current.terms-of- use#LAA Advanced Physical Techniques in Inorganic Chemistry: Probing Small Molecule Activation A dissertation presented by Bryce L. Anderson To The Department of Chemistry and Chemical Biology in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the subject of Chemistry Harvard University Cambridge, Massachusetts May 2016 © 2016 Bryce L. Anderson All rights reserved Dissertation Advisor: Professor Daniel G. Nocera Bryce L. Anderson Advanced Physical Techniques in Inorganic Chemistry: Probing Small Molecule Activation Abstract Robust and efficient catalysts are necessary for realizing chemical energy storage as a solution for the intermittency associated with renewable energy sources. To aid in the development of such catalysts, physical methods are used to probe the photochemistry of small molecule activation in the context of solar-to-fuels cycles. Three systems are studied in the context of HX splitting (X=Br, Cl): polypyridyl nickel complexes, NiX3(LL) (LL = bidentate phosphine) complexes, and dirhodium phosphazane complexes. -
Synthetic Advances in the C‐H Activation of Rigid Scaffold Molecules
Synthesis Review Synthetic Advances in the C‐H Activation of Rigid Scaffold Molecules Nitika Grovera Mathias O. Senge*a a School of Chemistry, Trinity College Dublin, The University of Dublin, Trinity Biomedical Sciences Institute, 152–160 Pearse Street, Dublin 2, Ireland [email protected] Dedicated to Prof. Dr. Henning Hopf Received: only recall the epic endeavors involved in Eaton’s cubane Accepted: Published online: synthesis,3 Parquette’s preparation of dodecahedrane, DOI: Prinzbach’s pagodane route thereto, or Maier’s synthesis of Abstract The remarkable structural and electronic properties of rigid non‐ tetra-tert-butyltetrahedrane.4 conjugated hydrocarbons afford attractive opportunities to design molecular building blocks for both medicinal and material applications. The bridgehead positions provide the possibility to append diverse functional groups at specific angles and in specific orientations. The current review summarizes the synthetic development in CH functionalization of the three rigid scaffolds namely: (a) cubane, (b) bicyclo[1.1.1]pentane (BCP), (c) adamantane. 1 Introduction 2 Cubane 2.1 Cubane Synthesis 2.2 Cubane Functionalization 3 BCP 3.1 BCP Synthesis 3.2 BCP Functionalization 4 Adamantane 4.1 Adamantane Synthesis 4.2 Adamantane Functionalization 5 Conclusion and Outlook Key words Cubane, bicyclo[1.1.1]pentane, adamantane, rigid scaffolds, CH‐ functionalization. Figure 1 The structures of cubane, BCP and adamantane and the five platonic hydrocarbon systems. The fascinating architecture of these systems significantly 1 Introduction differs from scaffolds realized in natural compounds. Hence, they attracted considerable attention from synthetic and The practice of synthetic organic chemistry of non-natural physical organic chemists to investigate their properties and to compounds with rigid organic skeletons provides a deep establish possible uses.3,5 Significantly, over the past twenty understanding of bonding and reactivity. -
Organogold Chemistry: Iiiapplications
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Springer - Publisher Connector Organogold Chemistry: IIIApplications R V Parish Department of Chemistry, UMIST, PO Box 88, Manchester M60 1QD, UK Gold forms a wide variety of organic derivatives, whose preparation, structures and reactions were reviewed in Parts I and II. Here some applications of the compounds are discussed, in the areas of organic synthesis, catalysis, liquid crystals, MOCVD, luminescence, and chemotherapy. Previous articles in this series have reviewed the diverse types of known organogold compounds (1) and the varied reactions which they undergo (2). Compared to those of other precious metals, compounds of gold feature in rather few applications, although interest has increased over recent years. In this contribution, these applications are reviewed, together with some suggestions for further developments. ORGANIC SYNTHESIS Some organogold compounds undergo reactions which give organic products which are useful or which cannot readily be obtained in other ways. For example, di-arylgold(III) compounds undergo reductive Box 1 Formation of biaryls, Ar-Ar’ elimination stimulated by addition of a tertiary phosphine, to give symmetric or unsymmetric diaryls (3). One of the aryl groups must have a substituent which also binds to the gold atom, in order to stabilize the di-aryl compound. A variety of other substituents may be present in either aryl. Some examples are shown in Box 1. Aryl- substituted ketones may be obtained similarly (4). The formation of homoallyl alcohols from aldehyde-insertion into the gold-carbon bonds of allyl, methallyl or crotyl complexes (5) is also useful, although isomerization sometimes means that the product is not that immediately expected (Box 2). -
Cheminformatics for Genome-Scale Metabolic Reconstructions
CHEMINFORMATICS FOR GENOME-SCALE METABOLIC RECONSTRUCTIONS John W. May European Molecular Biology Laboratory European Bioinformatics Institute University of Cambridge Homerton College A thesis submitted for the degree of Doctor of Philosophy June 2014 Declaration This thesis is the result of my own work and includes nothing which is the outcome of work done in collaboration except where specifically indicated in the text. This dissertation is not substantially the same as any I have submitted for a degree, diploma or other qualification at any other university, and no part has already been, or is currently being submitted for any degree, diploma or other qualification. This dissertation does not exceed the specified length limit of 60,000 words as defined by the Biology Degree Committee. This dissertation has been typeset using LATEX in 11 pt Palatino, one and half spaced, according to the specifications defined by the Board of Graduate Studies and the Biology Degree Committee. June 2014 John W. May to Róisín Acknowledgements This work was carried out in the Cheminformatics and Metabolism Group at the European Bioinformatics Institute (EMBL-EBI). The project was fund- ed by Unilever, the Biotechnology and Biological Sciences Research Coun- cil [BB/I532153/1], and the European Molecular Biology Laboratory. I would like to thank my supervisor, Christoph Steinbeck for his guidance and providing intellectual freedom. I am also thankful to each member of my thesis advisory committee: Gordon James, Julio Saez-Rodriguez, Kiran Patil, and Gos Micklem who gave their time, advice, and guidance. I am thankful to all members of the Cheminformatics and Metabolism Group. -
And Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes † † Kristian E
This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Review Cite This: Chem. Rev. 2019, 119, 2752−2875 pubs.acs.org/CR Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes † † Kristian E. Dalle, Julien Warnan, Jane J. Leung, Bertrand Reuillard, Isabell S. Karmel, and Erwin Reisner* Christian Doppler Laboratory for Sustainable SynGas Chemistry, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom ABSTRACT: The synthesis of renewable fuels from abundant water or the greenhouse gas CO2 is a major step toward creating sustainable and scalable energy storage technologies. In the last few decades, much attention has focused on the development of nonprecious metal-based catalysts and, in more recent years, their integration in solid-state support materials and devices that operate in water. This review surveys the literature on 3d metal-based molecular catalysts and focuses on their immobilization on heterogeneous solid-state supports for electro-, photo-, and photoelectrocatalytic synthesis of fuels in aqueous media. The first sections highlight benchmark homogeneous systems using proton and CO2 reducing 3d transition metal catalysts as well as commonly employed methods for catalyst immobilization, including a discussion of supporting materials and anchoring groups. The subsequent sections elaborate on productive associations between molecular catalysts and a wide range of substrates based on carbon, quantum dots, metal oxide surfaces, and semiconductors. The molecule−material hybrid systems are organized as “dark” cathodes, colloidal photocatalysts, and photocathodes, and their figures of merit are discussed alongside system stability and catalyst integrity. -
Chimica Industriale “Toso Montanari”
Alma Mater Studiorum - Università di Bologna SCUOLA DI SCIENZE Dipartimento di Chimica Industriale “Toso Montanari” Corso di Laurea Magistrale in Chimica Industriale Classe LM-71 - Scienze e Tecnologie della Chimica Industriale Supporting Cubane’s Renaissance: Metathesis reactions on 4-iodo-1-vinylcubane and Stetter reaction on 1-iodocubane-4-carboxaldehyde Tesi di laurea sperimentale CANDIDATO RELATORE Andrea Fasolini Chiar.mo Prof. Paolo RIghi CORRELATORE Prof. Mathias O. Senge ___________________________________________________________________________________________________________ _____________ Anno Accademico 2015-2016 ___________________________________________________________________________________________________________ _____________ 1 2 Abstract Cubane is a peculiar cube-shaped alkane molecule with a rigid, regular structure. This makes it a good scaffold, i.e. a molecular platform to which the substituents are arranged in a specific and fixed orientation. Moreover, cubane has a body diagonal of 2.72 Å, very similar to the distance across the benzene ring, i.e. 2.79 Å. Thus, it would be possible to use cubane as a scaffold in medicinal and material chemistry as a benzene isostere 1,2. This could lead to advantages in terms of solubility and toxicity and could provide novel properties. For this purpose, the possibility of performing “modern organic chemistry” on the cubane scaffold has to be studied. This project was entirely carried out in the framework of the Erasmus+ mobility programme at the Trinity College (Dublin, IRL) under the supervision of prof. M. O. Senge. The main goal of this project was to widen the knowledge on cubane chemistry. In particular, it was decided to test reactions that were never applied to the scaffold before, such as metathesis of 4-iodo-1-vinylcubane and Stetter reaction of 1-iodocubane-4- carboxaldehyde.