ACS Publications. Most Trusted. Most Cited. Most Read
Metal Cluster Stabilized Fluorenyl, Indenyl, and Cyclopentadienyl Antiaromatic Cations:  An NMR and X-ray Crystallographic Study

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Organometallics 1999, 18, 17, 3372-3382
    Article

    Metal Cluster Stabilized Fluorenyl, Indenyl, and Cyclopentadienyl Antiaromatic Cations:  An NMR and X-ray Crystallographic Study
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Chemistry, McMaster University, Hamilton, Ontario, Canada L8S 4M1
    Other Access OptionsSupporting Information (1)

    Organometallics

    Cite this: Organometallics 1999, 18, 17, 3372–3382
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om990292g
    Published July 30, 1999
    Copyright © 1999 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Treatment of fluorenone, 2,3-diphenylindenone, tetraphenylcyclopentadienone, or 2,5-diethyl-3,4-diphenylcyclopentadienone with ((trimethylsilyl)ethynyl)lithium gives, after hydrolysis, the analogous alkynol; subsequent addition of dicobalt carbonyl and then fluoroboric acid yields the corresponding fluorenyl, indenyl, or cyclopentadienyl cation stabilized by complexation to a tricarbonylcobalt moiety. Variable-temperature NMR data on these cluster cations, and on their bis(diphenylphosphino)methane derivatives, reveal that the barrier to migration of the cationic center between cobalt cluster vertices increases in the order fluorenyl < indenyl < cyclopentadienyl and suggest that the cations with more antiaromatic character have the greatest need for charge delocalization onto the metal center. Replacement of a Co(CO)3 cationic fragment by an Fe(CO)3 unit yields the mixed-metal species [((fluorenyl)CCSiMe3)FeCo(CO)6] (22) and [((2,3-diphenylindenyl)CCSiMe3)FeCo(CO)6] (27). In these structural models for the cationic complexes, the Fe−C(9) distance in 22 is 2.626(11) Å, while in the indenyl system 27 the Fe−C(1) distance is 2.347(7) Å, again indicating that the 8π indenyl cation interacts more strongly with the metal center than does the 12π fluorenyl cation.

    Copyright © 1999 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

    Supporting Information Available

    Click to copy section linkSection link copied!

    Tables of atomic parameters, including fractional atomic coordinates and equivalent isotropic displacement parameters, bond distances and angles, and anisotropic displacement parameters for the crystal structures of 22 and 27. This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 30 publications.

    1. Mariam A. Mehdi, Eric A. C. Bushnell, Sahar Nikoo, James W. Gauld, James R. Green. Generation and Reactions of a Benzodehydrotropylium Ion–Co2(CO)6 Complex. ACS Omega 2019, 4 (20) , 18600-18608. https://doi.org/10.1021/acsomega.9b02390
    2. Angela Moore, Yannick Ortin, Helge Müller-Bunz, and Michael J. McGlinchey. Alkynyl-Dicobalt Hexacarbonyl Complexes of Menthyl Cations: Isolobal Substitution of [Co(CO)3]+ by Fe(CO)3 as a Structural Model. Organometallics 2010, 29 (21) , 4882-4892. https://doi.org/10.1021/om100107x
    3. Sarah A. Brusey, Emilie V. Banide, Steffen Dörrich, Paul O’Donohue, Yannick Ortin, Helge Müller-Bunz, Conor Long, Paul Evans and Michael J. McGlinchey . X-ray Crystallographic and NMR Spectroscopic Study of (η2-Alkene)(μ-alkyne)pentacarbonyldicobalt Complexes: Arrested Pauson−Khand Reaction Intermediates. Organometallics 2009, 28 (21) , 6308-6319. https://doi.org/10.1021/om900615m
    4. Kohei Ogawa, Shinya Minegishi, Koichi Komatsu and Toshikazu Kitagawa. Generation and Reaction of a Phenyl-Substituted Cyclopentadienyl Cation Annelated with Two Homoadamantene Frameworks. The Journal of Organic Chemistry 2008, 73 (14) , 5248-5254. https://doi.org/10.1021/jo800340g
    5. Laura E. Harrington,, Ignacio Vargas-Baca,, Nada Reginato, and, Michael J. McGlinchey. Spectroscopic and Computational Assessment of the Rotational Barrier of a Ferrocenyl-Stabilized Cyclopentadienyl Cation:  Evidence for the First Hydroxyfulvalene Ligand. Organometallics 2003, 22 (4) , 663-669. https://doi.org/10.1021/om020820f
    6. James A. Dunn,, James F. Britten,, Jean-Claude Daran, and, Michael J. McGlinchey. Toward an Understanding of the Mechanism of Metal Exchange in (Propargyl Alcohol)Co2(CO)6 Clusters:  Syntheses and Structures of [η5-C5Ph2R2−C⋮C−TMS)(Fe(CO)2(μ-H)]Co2(CO)6, R = Ph or Et. Organometallics 2001, 20 (22) , 4690-4694. https://doi.org/10.1021/om010494o
    7. Annette D. Allen and, Thomas T. Tidwell. Antiaromaticity in Open-Shell Cyclopropenyl to Cycloheptatrienyl Cations, Anions, Free Radicals, and Radical Ions. Chemical Reviews 2001, 101 (5) , 1333-1348. https://doi.org/10.1021/cr990316t
    8. James A. Dunn,, Mark Stradiotto, and, Michael J. McGlinchey. Diels−Alder Adducts of 5-Alkynylcyclopentadienols with Tetracyanoethylene and Dimethyl Acetylenedicarboxylate:  An X-ray Crystallographic Study of Unexpected Rearrangement Products. The Journal of Organic Chemistry 2000, 65 (16) , 4861-4863. https://doi.org/10.1021/jo000125m
    9. James R. Green, Kenneth M. Nicholas, . Propargylic Coupling Reactions via Bimetallic Alkyne Complexes: The Nicholas Reaction. 2020, 931-1326. https://doi.org/10.1002/0471264180.or103.03
    10. Erich Kleinpeter, Andreas Koch. Paramagnetic ring current effects in anti-aromatic structures subject to substitution/annelation quantified by spatial magnetic properties (TSNMRS). Tetrahedron 2018, 74 (7) , 700-710. https://doi.org/10.1016/j.tet.2017.12.020
    11. Roman O. Iakovenko, Anna N. Kazakova, Irina A. Boyarskaya, Vladislav V. Gurzhiy, Margarita S. Avdontceva, Taras L. Panikorovsky, Vasiliy M. Muzalevskiy, Valentine G. Nenajdenko, Aleksander V. Vasilyev. Superacid‐Promoted Synthesis of CF 3 ‐Indenes Using Brominated CF 3 ‐Enones. European Journal of Organic Chemistry 2017, 2017 (37) , 5632-5643. https://doi.org/10.1002/ejoc.201701085
    12. Laura E. Harrington, James F. Britten, Michael Casey, John Grealis, Yannick Ortin, Helge Müller‐Bunz, Michael J. McGlinchey. Protonation of Tetraphenyl‐ and 2,3,4‐Triphenylcyclopentadienone – An NMR and X‐ray Crystallographic Study. European Journal of Organic Chemistry 2017, 2017 (22) , 3249-3255. https://doi.org/10.1002/ejoc.201700019
    13. Angela Moore, Johannes Ostermann, Helge Müller-Bunz, Yannick Ortin, Michael J. McGlinchey. Metal-stabilized carbocations derived from monoterpenes: dicobalt hexacarbonyl complexes of alkynyl-verbenols. Tetrahedron 2016, 72 (29) , 4186-4193. https://doi.org/10.1016/j.tet.2016.05.044
    14. Michelle Harris, Sarah A. Brusey, Angela Moore, Yannick Ortin, Helge Müller‐Bunz, Gabriele Manca, Carlo Mealli, Michael J. McGlinchey. [Co 2 (CO) 6 (Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?. ChemPlusChem 2016, 81 (3) , 292-306. https://doi.org/10.1002/cplu.201500477
    15. Christine Lepetit, Valérie Maraval, Yves Canac, Remi Chauvin. On the nature of the dative bond: Coordination to metals and beyond. The carbon case. Coordination Chemistry Reviews 2016, 308 , 59-75. https://doi.org/10.1016/j.ccr.2015.07.018
    16. Rahman Hosseinzadeh, Mohammadreza Khadem Abolfazli, Mojtaba Mohseni, Maryam Mohadjerani, Zahra Lasemi. Efficient Synthesis and Antibacterial Activities of Some Novel 1,2,3‐Triazoles Prepared from Propargylic Alcohols and Benzyl Azides. Journal of Heterocyclic Chemistry 2014, 51 (5) , 1298-1305. https://doi.org/10.1002/jhet.1680
    17. RAHMAN HOSSEINZADEH, MARYAM MOHADJERANI, MOHAMMAD JAVAD ARDESTANIAN, MOHAMMAD REZA NAIMI-JAMAL, ZAHRA LASEMI. Convenient synthesis of naphthopyrans using montmorillonite K-10 as heterogeneous catalyst. Journal of Chemical Sciences 2014, 126 (4) , 1081-1089. https://doi.org/10.1007/s12039-014-0670-4
    18. Sheida Amiralaei, James Gauld, James R. Green. Dehydrotropylium–Co 2 (CO) 6 Ion: Generation, Reactivity and Evaluation of Cation Stability. Chemistry – A European Journal 2011, 17 (15) , 4157-4165. https://doi.org/10.1002/chem.201002685
    19. Stephen P. Downing, Peter J. Pogorzelec, Andreas A. Danopoulos, David J. Cole‐Hamilton. Indenyl‐ and Fluorenyl‐Functionalized N‐Heterocyclic Carbene Complexes of Rhodium and Iridium – Synthetic, Structural and Catalytic Studies. European Journal of Inorganic Chemistry 2009, 2009 (13) , 1816-1824. https://doi.org/10.1002/ejic.200801162
    20. John H. Kaldis, Michael A. Brook, Michael J. McGlinchey. Solvent‐Mediated Generation of Cobalt‐Cluster‐Stabilised Propargyl Cations and Radicals: Allyl Migration versus Peroxide Formation. Chemistry – A European Journal 2008, 14 (32) , 10074-10084. https://doi.org/10.1002/chem.200801402
    21. Sheida Amiralaei, James R. Green. Generation and reactivity of the dehydrotropylium-Co2(CO)6 ion. Chemical Communications 2008, 58 (40) , 4971. https://doi.org/10.1039/b812174e
    22. Emilie V. Banide, Helge Müller‐Bunz, Anthony R. Manning, Paul Evans, Michael J. McGlinchey. X‐ray Crystal Structure of an Alkene–Pentacarbonyldicobalt–Alkyne Complex: Isolation of a Stable Magnus‐Type Pauson–Khand Reaction Intermediate. Angewandte Chemie 2007, 119 (16) , 2965-2968. https://doi.org/10.1002/ange.200605171
    23. Emilie V. Banide, Helge Müller‐Bunz, Anthony R. Manning, Paul Evans, Michael J. McGlinchey. X‐ray Crystal Structure of an Alkene–Pentacarbonyldicobalt–Alkyne Complex: Isolation of a Stable Magnus‐Type Pauson–Khand Reaction Intermediate. Angewandte Chemie International Edition 2007, 46 (16) , 2907-2910. https://doi.org/10.1002/anie.200605171
    24. Wing-Tak Wong. Heterometallic Iron-containing Compounds. 2007, 319-352. https://doi.org/10.1016/B0-08-045047-4/00090-X
    25. A.P. Sadimenko. Functions Containing Two Atoms of the Same Metallic Element. 2005, 627-671. https://doi.org/10.1016/B0-08-044655-8/00081-7
    26. A.P. Sadimenko. Functions Containing Two Atoms of Different Metallic Elements. 2005, 673-694. https://doi.org/10.1016/B0-08-044655-8/00082-9
    27. Yannick Ortin, Kirsten Ahrenstorf, Paul O'Donohue, Daniel Foede, Helge Müller-Bunz, Patrick McArdle, Anthony R. Manning, Michael J. McGlinchey. An NMR study of the rotational barriers in cobalt-stabilized carbocations: X-ray crystal structures of (η4-C4Ph4)Co-(η5-C5H4R), where R is CH3CO, CHO, CH(tBu)OH. Journal of Organometallic Chemistry 2004, 689 (9) , 1657-1664. https://doi.org/10.1016/j.jorganchem.2004.02.021
    28. James A Dunn, Laura E Harrington, Michael J McGlinchey. The alkyne-anion promoted ring-contraction of hexachlorotropone: synthesis and structure of [trimethylsilyl(pentachlorobenzoyl)ethyne]-hexacarbonyldicobalt. Journal of Organometallic Chemistry 2004, 689 (1) , 8-13. https://doi.org/10.1016/j.jorganchem.2003.09.033
    29. Michael J McGlinchey. 2000 Alcan Award Lecture Adventures in organometallic NMR: steric restraints, slowed rotations, and skeletal rearrangements. Canadian Journal of Chemistry 2001, 79 (9) , 1295-1309. https://doi.org/10.1139/v01-117
    30. Xavier Creary, Allison Wolf. Effect of oxime substituents on 9-fluorenyl carbocations. Journal of Physical Organic Chemistry 2000, 13 (6) , 337-343. https://doi.org/10.1002/1099-1395(200006)13:6&lt;337::AID-POC249&gt;3.0.CO;2-T
    Download PDF
    Go to Organometallics
    Get e-Alerts
    Get e-Alerts

    Organometallics

    Cite this: Organometallics 1999, 18, 17, 3372–3382
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om990292g
    Published July 30, 1999
    Copyright © 1999 American Chemical Society
    Request reuse permissions

    Article Views

    330

    Altmetric

    -

    Citations

    30
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.