DOCSLIB.ORG

Synthesis, Characterization and Reactions of Complexes Containing New Ligands with Carbon- Phosphorus Multiple Bonds Wayde Vincent Konze Iowa State University

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis, Characterization and Reactions of Complexes Containing New Ligands with Carbon- Phosphorus Multiple Bonds Wayde Vincent Konze Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1997 Synthesis, characterization and reactions of complexes containing new ligands with carbon- phosphorus multiple bonds Wayde Vincent Konze Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Konze, Wayde Vincent, "Synthesis, characterization and reactions of complexes containing new ligands with carbon-phosphorus multiple bonds " (1997). Retrospective Theses and Dissertations. 11999. https://lib.dr.iastate.edu/rtd/11999 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI fihns the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely afreet reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper lefr-hand comer and continuing from left to right in equal sections with small overlaps. Each original is also photographed m one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. UMI A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor MI 48106-1346 USA 313/761-4700 800/521-0600 Synthesis, characterization and reactions of complexes containing ligands with carbon-phosphorus multiple bonds by Wayde Vincent Konze A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major; Inorganic Chemistry Major Professor: Robert J. Angelici Iowa State University Ames, Iowa 1997 T]MI Niamber: 9814659 UMI Microform 9814659 Copyright 1998, by UMI Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 Graduate College Iowa State University This is to certify that the Doctoral dissertation of Wayde Vincent Konze has met the thesis requirements of Iowa State University Signature was redacted for privacy. Major Professor Signature was redacted for privacy. For the Major Program Signature was redacted for privacy. For the Graduate College Ill To my family, who have given me love, life and the comfort of a milestone from which I may always know how far I have come and how far there is yet to go: Rebecca Ann, Nicolette Amber and Joseph Allen Konze IV TABLE OF CONTENTS ABBREVIATIONS vi GENERAL INTRODUCTION I Dissertation Organization 1 Literature Review I References 20 NICKEL COMPLEXES CONTAINING NEW CARBON-PHOSPHORUS UNSATURATED LIGANDS: FIRST EXAMPLES OF PHOSPHAVINYLIDENE- PHOSPHORANE [R3P=C=PR'] AND PHOSPHAVINYL PHOSPHONIUM [C(H)(PR3)=P(R')]* LIGANDS 25 Abstract 25 Introduction 26 Experimental Section 29 Results 36 Discussion 43 Summary 55 Acknowledgment 56 References 56 PALLADIUM COORDINATION COMPOUNDS OF ct'A.^-PHOSPHORANES: FIRST EXAMPLES OF PH0SPH0NI0-METHYLENE(IMIN0)METALL0- PHOSPHORANE [(R3P)(Me3Si)C=P(ML„)=NSiMe3] AND PHOPHONIO- METHYLENE(0X0)PH0SPH0RANE [(R3P)(Me3Si)C=P(=0)NSiMe3] LIGANDS 70 Abstract 70 V Introduction 71 Experimental Section 74 Results 82 Discussion 90 Conclusion 99 Acknowledgment 102 References 102 FUNCTIONALIZATION OF n'-BRIDGING CYAPHIDE (C=F) LIGANDS: TRINUCLEAR n', n", ii'-BRIDGING CYAPHIDE AND DINUCLEAR BRIDGING ISOCYAPHIDE (C=PR) COMPLEXES OF PLATINUM 112 Abstract 112 Introduction 113 Results and Discussion 115 Summary 129 Experimental Section 130 Acknowledgment 137 References 138 GENERAL SUMMARY 149 ACKNOWLEDGMENTS 151 vi ABBREVIATIONS Mes*, 2,4,6-tri-ferf-butylbenzene Mes, 2,4,6-tri-methylbenzene xyl, 2,6-dimethylbenzene COD, 1,5-cyclooctadiene Cp, ri^-CjHj ligand Cp*, ri^-CsMes ligand Me, -CH3 group Et, -CH2CH3 i-Pr, -CHCCHj), t-Bu, -CCCHj), Ph, -CgH; group Cy, -CgH,, group Bn, -CHjPh dppm, Ph^PCHiPPhj dppe, PhjPCH.CH.PPh, dba, dibenzylideneacetone 1 GENERAL INTRODUCTION Dissertation Organization This dissertation contains three papers in the format required for journal publication, describing the research I performed at Iowa State University. Preceding these papers is a literature review of 7c-complexation of carbon-phosphorus double and triple bonds. In the literature review as well as the papers, the literature citations, schemes, tables and figures pertain only to the chapters in which they appear. After the final paper is a general summary. Literature Review Introduction The field of carbon-phosphorus multiply bonded compounds has seen remarkable growth in a relatively short period of time. These compounds violate the outdated "double bond rule" which stated that 4th and 5th row main group elements should not be capable of fonning multiple bonds. This reluctance to take part in multiple bond formation is a manifestation of the inert s-pair effect in higher main group elements; ^ the s-orbitals are contracted due to the greater nuclear charge and this spatial inequity between the s and p- orbitals makes the formation of hybrid orbitals less favored, even though the energy differences between the s and p-orbitals in 4th and 5th row main group elements are comparable to those in second row elements. Although C=P n-bonds are calculated to be 22.3 kcal/mol less stable than C=C ic-bonds,^ Becker was able to isolate the first example of a stable phosphaalkene compound^ in 1976 by incorporating bulky R-groups on the carbon and phosphorus atoms in order to kinetically stabilize the reactive C=P double bond. Since this discovery, many examples of stable phosphaalkene and other interesting C=P containing 2 compounds have been reported and the coordination chemistry of these compounds has developed at a very rapid pace. Theoretical calculations and photoelectron studies on MeP=CH2 have shown that the HOMO consists mainly of the C=P jc-orbital and that the LUMO consists mainly of the relatively low lying C=P n* orbital.^-^ Consequendy, compounds containing C-P multiple bonds have shown a rich olefin-like ^^-coordination chemistry. In fact, complexes containing C-P multiple bond analogs of almost all C-C multiple bond ligands are known, including phosphaalkenes, phosphaalkynes, phosphaallyls, phosphaallenes, phosphabutadienes, phosphacyclopropenes, phosphacyclobutadienes, phosphacyclopentadienyls and phosphaarenes.^"^ All of these C-P multiple bond ligands exhibit the ability to coordinate to metals through the C-P re-system, and offer the additional coordination site of the phosphorus lone pair as well. The ^'P NMR spectroscopy of these ligands has proven useful for structure elucidation and bonding explanations and is a very important diagnostic tool. Although these 7c-bonded C-P multiple bond ligands are in many cases analogous to their carbon counterparts, they also exhibit important differences which have allowed them to become more than just phosphorus analogs of common ligands. Unlike commonly tetravalent carbon, phosphorus is able to form mono, di, tri, tetra, penta and hexavalent compounds, which has allowed for the coordination of several C-P multiple bond ligands that have no analogs in carbon chemistry. This review covers structure and bonding aspects of 7i-complexes of carbon- phosphorus unsaturated ligands in the literature through the middle of 1997. TI^-Phosphaalkene (R2C=PR) Complexes Both ab initio STO/3G calculations and'^''^ photoelectron spectroscopic results on phosphaalkenes indicate that the o-phosphorus lone pair and the C=P Tc-orbitals are very close in energy, with the re-orbital as the HOMO in the parent compound CH,=PH. These results suggest that phosphaalkenes should be capable of coordination either r\- through the C=P 3 double bond or ri' through the phosphorus lone pair, both of which have been accomplished in practice; there are several examples of complexes containing TI'-P coordinated or ri"-C=P coordinated phosphaalkenes, as well as mixed, n', n'-coordinated phosphaalkenes.^'^® There are also a few examples of cluster-stabilized phosphaalkenes with the phosphaalkene bridging between several metals.^'The majority of these complexes have been prepared by displacing weakly coordinating ligands on a transition metal complex with stable phosphaalkene ligands. Both steric and electronic factors determine whether the phosphaalkene Ligands will coordinate ii' or n' to a transition metal complex; electron-rich metal centers are better
Load more

Recommended publications
  • Novel Alkyne and Phosphaalkyne Coupling on an Ir4 Cluster: Synthesis and Molecular Structure of [Ir4(P-CO)(CO)7{P4-T13-Ph,PC(H)C(Ph)Pcbut}(P-Pph2)1 Maria Helena A
    View Article Online / Journal Homepage / Table of Contents for this issue J. CHEM. SOC., CHEM. COMMUN., 1994 1869 Novel Alkyne and Phosphaalkyne Coupling on an Ir4 Cluster: Synthesis and Molecular Structure of [Ir4(p-CO)(CO)7{p4-t13-Ph,PC(H)C(Ph)PCBut}(p-PPh2)1 Maria Helena A. Benvenutti,asb Peter B. Hitchcock,b John F. Nixon*b and Maria D. Vargas*d a lnstituto de Quimica, Universidade Estadual de Campinas, CP 6154, Campinas, 13083, SP, Brazil b School of Chemistry and Moiecular Sciences, University of Sussex, Brighton, UK BN 1 9QJ The cluster compound [(p-H)Ir4(CO),(Ph2PCCPh)(p-PPh2)]1 reacts with the phosphaalkyne ButCP to yield [Ir4(p-CO)(CO),{p~-113-Ph2PC(H)C(Ph)PCBut}(p-PPh2)]3, containing the novel 2-phosphabutadienylphosphine fragment as a result of the coupling of ButCP with the diphenylphosphinoalkyne ligand and incorporation of the cluster bound H atom. There are relatively few examples of controlled alkyne-alkyne between the Ph2PCCPh ligand and the ButCP molecule, and coupling reactions at polynuclear carbonyl clusters.' The hydride migration to the resulting new phosphorus carbon chemistry of phosphaalkynes, RCP, is of considerable con- chain were established by 'H, 31P and 13C NMR spectroscopy. temporary interest and their similarity to alkynes has been In spite of the detailed spectroscopic studies undertaken, it stressed previously.2 There is only one reported interaction was impossible to establish unambiguously the position of the between an alkyne and a phosphaalkyne, leading to a hydrogen atom in the chain, and whether the diphenylphos- mononuclear 774-1-phosphacyclobutadienecomplex described phinoalkyne had undergone P-C,, bond cleavage.
    [Show full text]
  • Intermediate Oxidation State Tungsten Acetylacetonate Complexes
    Intermediate Oxidation State Tungsten Acetylacetonate Complexes Chetna Khosla A dissertation submitted to the faculty of the University of North Carolina at Chapel Hill in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry. Chapel Hill 2009 Approved by: Advisor: Professor Joseph L. Templeton Reader: Professor Maurice Brookhart Reader: Professor Cynthia Schauer Professor Valerie Ashby Professor H. Holden Thorp ABSTRACT Chetna Khosla: INTERMEDIATE OXIDATION STATE TUNGSTEN ACETYLACETONATE COMPLEXES (Under the direction of Professor Joseph L. Templeton) Previous work with tungsten(II) acetylacetonate complexes has focused on synthesis of complexes with -bound ligands (alkyne, nitrile, imine, ketone, aldehyde). In this work, 2 addition of methyl triflate (MeOTf) to W(CO)(acac)2(η -N≡CPh) produces the iminoacyl 2 complex [W(CO)acac)2(η -MeN=CPh)][OTf]. Displacement of the carbon monoxide in 2 + [W(CO)(acac)2(η -MeN≡CPh)] by isonitriles, bulky phosphines, and alkynes has been accomplished. The substitution of carbon monoxide by alkyne relieves the iminoacyl ligand of its role as a four-electron donor and enables further reduction of the C-N based ligand. Use 2 + of Na[HB(OMe)3] as a hydride source that attacks [W(RC≡CR′)(acac)2(η -MeN=CPh)] 2 yields the imine complex W(RC≡CR′)(acac)2(η -MeN=CHPh) with a diastereoselective ratio of 2:1. Addition of MeOTf leads to the final tungsten(II) iminium complex 2 [W(RC≡CR′)(acac)2(η -Me2N=CHPh)][OTf]. 2 Addition of m-chloroperoxybenzoic acid (MCPBA) to W(CO)(acac)2(η -N≡CR) 2 2 results in oxidation of the metal center to form the W(IV) d metal complex W(O)(acac)2(η - N≡CR).
    [Show full text]
  • Lowcoordinated Silicon and Hypercoordinated Carbon
    Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 557 Lowcoordinated Silicon and Hypercoordinated Carbon Structure and Stability of Silicon Analogs of Alkenes and Carbon Analogs of Silicates ANDERS M. EKLÖF ACTA UNIVERSITATIS UPSALIENSIS ISSN 1651-6214 UPPSALA ISBN 978-91-554-7294-8 2008 urn:nbn:se:uu:diva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
    [Show full text]
  • Conjugated Low Coordinate Organophosphorus Materials
    CONJUGATED LOW COORDINATE ORGANOPHOSPHORUS MATERIALS: SYNTHESIS, CHARACTERIZATION AND PHOTOCHEMICAL STUDIES By VITTAL BABU GUDIMETLA Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Thesis Advisor: Dr. John D. Protasiewicz Department of Chemistry CASE WESTERN RESERVE UNIVERSITY January, 2010 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation of _____________________________________________________ candidate for the ______________________degree *. (signed)_______________________________________________ (chair of the committee) ________________________________________________ ________________________________________________ ________________________________________________ ________________________________________________ ________________________________________________ (date) _______________________ *We also certify that written approval has been obtained for any proprietary material contained therein. Dedicated to my parents Table of Contents List of Tables………………………………………………………………………………i List of Figures…………………………………………………………………………….iii List of Charts…………………………………………………………………………….vii List of Schemes……………………………………………………………………………x List of Abbreviations…………………………………………………………………….xii Acknowledgement………………………………………………………………………xiv Abstract…………………………………………………………………………………xvi Chapter 1. Introduction 1.1 Conjugated Organic Materials: General Introduction …………….………1 1.2 Mutiple (pπ-pπ ) Bonding in Main Group Elements: Brief Historical Background………………………………………………………………..3
    [Show full text]
  • Throughconjugation of Two Phosphaalkyne ('CP') Moieties
    Through-conjugation of two phosphaalkyne (`CP') moieties mediated by a bimetallic scaffold² Article (Published Version) Leech, Matthew C and Crossley, Ian R (2018) Through-conjugation of two phosphaalkyne (‘CP’) moieties mediated by a bimetallic scaffold†. Dalton Transactions, 47. pp. 4428-4432. ISSN 1477- 9226 This version is available from Sussex Research Online: http://sro.sussex.ac.uk/id/eprint/74320/ This document is made available in accordance with publisher policies and may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher’s version. Please see the URL above for details on accessing the published version. Copyright and reuse: Sussex Research Online is a digital repository of the research output of the University. Copyright and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable, the material made available in SRO has been checked for eligibility before being made available. Copies of full text items generally can be reproduced, displayed or performed and given to third parties in any format or medium for personal research or study, educational, or not-for-profit purposes without prior permission or charge, provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. http://sro.sussex.ac.uk Dalton Transactions View Article Online COMMUNICATION View Journal | View Issue Through-conjugation of two phosphaalkyne (‘CuP’) moieties mediated by a bimetallic Cite this: Dalton Trans., 2018, 47, 4428 scaffold † Received 10th January 2018, Accepted 6th February 2018 Matthew.
    [Show full text]
  • Group Multiple Bonds for Bond Activations and Catalysis Catherine Weetman*[A]
    Minireview Chemistry—A European Journal doi.org/10.1002/chem.202002939 & Main Group Elements |Reviews Showcase| Main Group Multiple Bonds for Bond Activations and Catalysis Catherine Weetman*[a] Chem. Eur. J. 2020, 26,1–15 1 2020 The Authors. Published by Wiley-VCH GmbH && These are not the final page numbers! ÞÞ Minireview Chemistry—A European Journal doi.org/10.1002/chem.202002939 Abstract: Since the discovery that the so-called “double- thermore, whilst their ability to act as transition metal bond” rule could be broken, the field of molecular main mimics has been explored, their catalytic behaviour is some- group multiple bonds has expanded rapidly. With the major- what limited. This Minireview aims to highlight the potential ity of homodiatomic double and triple bonds realised within of these complexes towards catalytic application and their the p-block, along with many heterodiatomic combinations, role as synthons in further functionalisations making them a this Minireview examines the reactivity of these compounds versatile tool for the modern synthetic chemist. with a particular emphasis on small molecule activation. Fur- Introduction On descending the group the stability of the lower oxidation state increases and thus its desire to partake in bond forma- Molecular main group multiple bond chemistry has rapidly de- tion decreases. For example in group 14, SnII is more stable veloped since the isolation of the first silicon-silicon double than SnIV, whilst for the lightest congener CIV is more stable bond. West’s disilene[1] broke the so called “double-bond” rule, than CII. This can also influence the complex formation in both in which it was thought that p-block elements with a principal the solution and solid state as highlighted by Lappert’s quantum number greater than two (i.e.
    [Show full text]
  • L3C3P3: Tricarbontriphosphide Tricyclic Radicals and Cations
    Author Manuscript Title: L3C3P3: Tricarbontriphosphide Cage Radicals and Cations Stabilized by Cy- clic (alkyl)(amino)carbenes Authors: Hansjorg¨ Grutzmacher,¨ Prof.; Zhongshu Li; Yuanfeng Hou; Yaqi Li; Alexan- der Hinz; Jeffrey Harmer; Chen-Yong Su; Guy Bertrand This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofrea- ding process, which may lead to differences between this version and the Version of Record. To be cited as: 10.1002/ange.201710099 Link to VoR: https://doi.org/10.1002/ange.201710099 L3C3P3: Tricarbontriphosphide Cage Radicals and Cations Stabilized by Cyclic (alkyl)(amino)carbenes Zhongshu Li,[a] Yuanfeng Hou,[a] Yaqi Li,[a] Alexander Hinz,[b] Jeffrey R. Harmer,*[c] Cheng-Yong Su,[a] Guy Bertrand,[e] and Hansjörg Grützmacher*[a,d] [a] Dr. Z. Li, Y. Hou, Y. Li, Prof. Dr. C.-Y. Su, Lehn Institute of Functional Materials (LIFM) School of Chemistry Sun Yat-Sen University 510275 Guangzhou, China E-mail: [email protected] [b] Dr. A. Hinz University of Oxford, Chemistry Research Laboratory 12 Mansfield Road, OX1 3TA, Oxford, UK E-mail: [email protected] [c] Assoc. Prof. Dr. J. R. Harmer. Centre for Advanced Imaging, University of Queensland, Brisbane, QLD, 4072, Australia E-mail: [email protected] [d] Prof. Dr. H. Grützmacher Department of Chemistry and Applied Biosciences ETH Zurich 8093 Zurich, Switzerland E-mail: [email protected] [e] Prof. Dr. G. Bertrand UCSD/CNRS Joint Research Chemistry Laboratory Department of Chemistry University of California San Diego La Jolla, CA 92521–0403, USA E-mail: [email protected] 1 This article is protected by copyright.
    [Show full text]
  • Throughconjugation of Two Phosphaalkyne ('CP') Moieties
    Through-conjugation of two phosphaalkyne (`CP') moieties mediated by a bimetallic scaffold² Article (Accepted Version) Leech, Matthew C and Crossley, Ian R (2018) Through-conjugation of two phosphaalkyne (‘CP’) moieties mediated by a bimetallic scaffold†. Dalton Transactions, 47. pp. 4428-4432. ISSN 1477- 9226 This version is available from Sussex Research Online: http://sro.sussex.ac.uk/id/eprint/74320/ This document is made available in accordance with publisher policies and may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher’s version. Please see the URL above for details on accessing the published version. Copyright and reuse: Sussex Research Online is a digital repository of the research output of the University. Copyright and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable, the material made available in SRO has been checked for eligibility before being made available. Copies of full text items generally can be reproduced, displayed or performed and given to third parties in any format or medium for personal research or study, educational, or not-for-profit purposes without prior permission or charge, provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. http://sro.sussex.ac.uk Please do not adjust margins Journal Name COMMUNICATION Through-conjugation of Two Phosphaalkyne (‘C ≡≡≡P’) Moieties Mediated by a Bimetallic Scaffold† Received 00th January 20xx, Accepted 00th January 20xx Matthew.
    [Show full text]
  • Chapter 1. Introduction
    Research Collection Doctoral Thesis Alkoxide packaged sodium dihydrogenphosphide synthesis and reactivity Author(s): Hendriksen, Coenradus Johannes Hendrikus Publication Date: 2012 Permanent Link: https://doi.org/10.3929/ethz-a-007333135 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library Dissertation ETH No. 20148 Alkoxide Packaged Sodium Dihydrogenphosphide: Synthesis and Reactivity A dissertation submitted to ETH Zurich for the degree of Doctor of Sciences Presented by Coenradus Johannes Hendrikus Hendriksen MSc. Radboud University Nijmegen Born 29th March 1981 Citizen of the Netherlands Accepted on the recommendation of Prof. Dr. H. Grützmacher, examiner Prof. Dr. A. Togni, co-examiner 2012 "Lucifer revealed the shining day and night fled." Ovid, Metamorphoses 8. 1 ff (trans. Melville) (Roman epic C1st B.C. to C1st A.D.) Abstract This work aims to describe the activation of white phosphorus to form highly functionalized compounds. White phosphorus is used as starting material as it is a highly reactive and selective reagent. From white phosphorus new synthesis routes towards sodium dihydrogenphosphide were developed. Previous routes towards sodium dihydrogenphosphide were dangerous and laborious. In this work new procedures are described to synthesize sodium dihydrogenphosphide conveniently at room temperature and apply them on a large scale not requiring high pressures or special equipment. By determining intermediates in the formation of sodium dihydrogenphosphide reaction mechanisms were elucidated. Functionalization of prepared sodium dihydrogenphosphide was of primary interest. In a procedure described by Stein et al. bis(mesitoyl)phosphide was synthesized with sodium dihydrogenphosphide.
    [Show full text]
  • Complexes of Dichlorogermylene with Phosphine/Sulfoxide-Supported Carbone As Ligand †
    molecules Article Complexes of Dichlorogermylene with Phosphine/Sulfoxide-Supported Carbone as Ligand † Ugo Authesserre 1 , Sophie Hameury 1,2, Aymeric Dajnak 1, Nathalie Saffon-Merceron 3, Antoine Baceiredo 1, David Madec 1,* and Eddy Maerten 1,* 1 Université de Toulouse, UPS, and CNRS, LHFA UMR 5069, 118 Route de Narbonne, 31062 Toulouse, France; [email protected] (U.A.); [email protected] (S.H.); [email protected] (A.D.); [email protected] (A.B.) 2 Université de Poitiers, IC2MP, UMR CNRS 7285, 1 Rue Marcel Doré, CEDEX 9, 86073 Poitiers, France 3 Université de Toulouse, UPS, and CNRS, ICT UAR2599 118 Route de Narbonne, 31062 Toulouse, France; [email protected] * Correspondence: [email protected] (D.M.); [email protected] (E.M.) † This paper is dedicated to the memory of Professor André Mortreux. Abstract: Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L2C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs. In this context, the phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene. Two original stable coordination complexes were obtained and fully characterized in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis, respectively. At 60 ◦C, in the presence of 4, the Ge(II)-complex 5 undergoes a slow isomerization that transforms the bis-ylide ligand into an yldiide. Citation: Authesserre, U.; Hameury, S.; Dajnak, A.; Saffon-Merceron, N.; Keywords: carbone; ligand; germylene; coordination; ylide Baceiredo, A.; Madec, D.; Maerten, E.
    [Show full text]
  • Two-Armed Silicon
    NEWS & VIEWS RESEARCH INORGANIC CHEMISTRY (109.7°), perhaps implying that their silylene is more reactive than Rekken and colleagues’ compound. Both silylenes exhibit striking thermal Two-armed silicon stability for divalent silicon compounds: Rekken and colleagues’ compound is stable up Compounds of transition metals are often used to activate small molecules for to 146 oC, whereas Protchenko and colleagues’ chemical reactions. The discovery of unusual silicon-containing compounds compound is stable up to 130 oC. The stability raises the prospect of metal-free activators. of the new silylenes must be due largely to steric protection of the reactive silicon atoms by the attached groups (in other words, the bulky ROBERT WEST from a starting material that was structurally groups shield the silicon atoms from attack identical to the silylene product, but in which by other molecules). The bulky groups might ny chemist will tell you that silicon two bromine atoms were also attached to the also stabilize the compounds by donating atoms are tetravalent — that is, they silicon atom. They removed the two bromine electrons to the silicon atom. have four electrons available for atoms using a magnesium-containing reduc- Further insight into the chemical bonding Achemical bonding, and therefore usually form ing agent. in the two silylenes was obtained by looking at four single bonds to other atoms. But two In the second paper2, Protchenko and col- the signals (the chemical shifts) of silicon-29 papers1,2 published in the Journal of the Am­­ leagues’ silylene (Fig. 1b) has a more complex nuclei in the nuclear magnetic resonance eri can Chemical Society report some remark- structure than Rekken and colleagues’ com- spectra for the molecules.
    [Show full text]
  • Methylidyne Transfer Reactions with Niobium † ‡ † Takashi Kurogi, Balazs Pinter, and Daniel J
    Communication Cite This: Organometallics 2018, 37, 3385−3388 Methylidyne Transfer Reactions with Niobium † ‡ † Takashi Kurogi, Balazs Pinter, and Daniel J. Mindiola*, † Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States ‡ Department of Chemistry, Universidad Tecnicá Federico Santa María, Valparaíso 2390123, Chile *S Supporting Information ABSTRACT: The mononuclear niobium methylidyne − i [(PNP)(ArO)Nb CH] (1; PNP = N[2-P Pr2-4-methyl- − i phenyl]2 , Ar = 2,6- Pr2C6H3) reacts with the isocyanate O CNtBu to form a mononuclear niobium oxo species with a rare example of an azaallenyl ligand, namely [(PNP)(ArO)- NbO(CHCNtBu)] (2). When 1 is treated with the phosphaalkyne PCAd (Ad = 1-adamantyl), PC bond cleavage occurs to form a mononuclear complex where P−P coupling has occurred between the formal phosphaalkyne phosphorus atom and one phosphine arm from the PNP ligand, namely [(PNPP)(ArO)Nb(η2-AdCCH)] (3). Solid- state structural studies and isotopic labeling experiments confirm C−C bond formation of the methylidyne group as well as provide conclusive evidence for the oxo ligand in 2 being terminal and the fate of the phosphorus atom from PCAd in complex 3. Computational studies have been applied to understand the pathway involving the P−P bond forming reaction of 1 and PCAd. igh-valent (d0) transition-metal methylidyne complexes CNtBu in toluene over 15 min resulted in clean formation of are extremely rare and are generally confined to the the mononuclear oxo complex [(PNP)(ArO)NbO(CH H − 3 t heavier group 6 metals, such as ([N3N]W CH) (N3N = CN Bu)] (2), isolated in 65% yield as a reddish orange 3− 1 12 13 [RNCH2CH2]3N ,R=Me3Si, Me2PhSi, MePh2Si, C6F5), material (Scheme 1).
    [Show full text]