{"id":11450,"date":"2013-10-26T08:26:53","date_gmt":"2013-10-26T07:26:53","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=11450"},"modified":"2016-02-11T07:53:00","modified_gmt":"2016-02-11T07:53:00","slug":"the-nmr-spectra-of-methano10annulene-and-its-dianion-the-diatropicparatropic-inversion","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=11450","title":{"rendered":"The NMR spectra of methano[10]annulene and its dianion. The diatropic\/paratropic inversion."},"content":{"rendered":"
\n

\n\tThe 1<\/sup>H NMR spectrum of an aromatic molecule such as benzene is iconic; one learns that the unusual chemical shift of the protons (~δ 7-8 ppm) is due to their deshielding by a diatropic<\/strong> ring current resulting from the circulation of six aromatic π-electrons following the Hückel 4n+2<\/span> rule. But rather less well-known is the spectacular inversion of these effects as induced by the paratropic <\/strong>circulation of 4n<\/span> electrons. A 4n+2 rule can be converted to a 4n one by the addition of two electrons, and chemically this can be done by reduction with lithium metal<\/a> to form a dianion. Fortunately, this experiment has been done for a molecule known as methano[10]annulene<\/em>. This is a 4n+2 aromatic molecule 1<\/strong> with ten<\/a> π-electrons (n=2) that can be reduced with lithium metal to form an ion-pair 2<\/strong> comprising lithium cations and the twelve π-electron (4n, n=3) methano[10]annulene dianion<\/em>.[1]<\/a><\/span>\n<\/p>\n

\n\tHere I ask whether these magnetic effects can be modelled using quantum mechanics. The point of interest here is the ion-pair<\/a>. Can one get away with simply modelling the di-anion in say a continuum solvent (thf), or is the nearby presence of lithium cations (variously solvated) essential? \"dianion\"<\/a>\n<\/p>\n

\n\t I used the model ωB97XD\/TZVP\/SCRF=THF (this DFT functional was shown to give good results for Rebek's encapsulated methane<\/a>, itself manifesting lots of diamagnetic effects from the benzo groups of the capsule). Several models 3-6 for the di-anion were explored:\n<\/p>\n

    \n
  1. \n\t\tA negatively charged species, stabilised by continuum solvation (thf).\n\t<\/li>\n
  2. \n\t\tA neutral species, with two naked Li cations bound to the under face of the annulene\n\t<\/li>\n
  3. \n\t\tSame as 4, but with one water molecule in the remaining coordination sphere of the Li.\n\t<\/li>\n
  4. \n\t\tSame as 4, but with two MeOMe molecules in the remaining coordination sphere of the Li.\n\t<\/li>\n
  5. \n\t\tModels 4-6 relate to what is called an intimate ion-pair (also a contact ion pair). We are not exploring the solvent-separated variety here.\n\t<\/li>\n<\/ol>\n

    \n\tI should also note that whereas the methane[10]annulene itself has C2v<\/sub> symmetry, the di-anion has the lower C2<\/sub> symmetry, since the bond lengths are no longer approximately equal, a well known consequence<\/a> of anti-aromaticity and associated paratropicity. Model 6 is shown below. It corresponds to two allyl anion.lithium cation ion pairs, separated by two localized double bonds.\n<\/p>\n

    \"Click

    Click for 3D<\/p><\/div>\n

    \n\tThe NMR for 1<\/strong> and 2<\/strong> and the models 3-6<\/strong> is shown below. The shifts computed for the dianion are the average of two equilibrating forms, the barrier to which is fast on the NMR time scale. It would be fair to say that overall, the chemical shifts computed for the ion-pair model are a better fit to the recorded spectra than the purely anionic model. The most realistic ion-pair model, in which the lithium is also coordinated to two (dimethyl) ether oxygens, is a fair, if not perfect fit. Realistically in solution a number of dynamically equilibrating arrangements of the ion pair, possibly solvated by more ethers, or even to the extent of creating a solvent separated ion-pair, probably contribute to the overall Boltzmann populations.\n<\/p>\n\n\n\n\n\n\n\n\n\n\n\n
    \n\t\t\t\t <\/span>\n\t\t\t<\/th>\n\n\t\t\t\t1<\/sup>H<\/span>\n\t\t\t<\/th>\n\n\t\t\t\t13<\/sup>C<\/span>\n\t\t\t<\/th>\n<\/tr>\n
    \n\t\t\t\tsystem\/model<\/strong><\/span>\n\t\t\t<\/td>\n\n\t\t\t\tδ2,5,7,10<\/sub><\/span>\n\t\t\t<\/td>\n\n\t\t\t\tδ3,4,8,9<\/sub><\/span>\n\t\t\t<\/td>\n\n\t\t\t\tδ11<\/sub><\/span>\n\t\t\t<\/td>\n\n\t\t\t\tδ2,5,7,10<\/sub><\/span>\n\t\t\t<\/td>\n\n\t\t\t\tδ3,4,8,9<\/sub><\/span>\n\t\t\t<\/td>\n\n\t\t\t\tδ1,6<\/sub><\/span>\n\t\t\t<\/td>\n\n\t\t\t\tδ11<\/sub><\/span>\n\t\t\t<\/td>\n<\/tr>\n
    \n\t\t\t\t 1<\/strong>[1]<\/a><\/span><\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 7.27<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 6.95<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t -0.52<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 128.7<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 126.1<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 114.6<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 34.8<\/span>\n\t\t\t<\/td>\n<\/tr>\n
    \n\t\t\t\t 1(calc)[2]<\/a><\/span><\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 7.93<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 7.58<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t -0.86<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 137.0<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 133.3<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 121.2<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 37.3<\/span>\n\t\t\t<\/td>\n<\/tr>\n
    \n\t\t\t\t 2<\/strong> expt dianion[1]<\/a><\/span><\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 1.59<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 3.07<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 11.64<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 76.5<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 118.0<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 165.0<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 60.0<\/span>\n\t\t\t<\/td>\n<\/tr>\n
    \n\t\t\t\t 3(2–<\/sup>)[3]<\/a><\/span><\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 2.45<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 2.78<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 10.75<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 90.4<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 105.1<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 155.1<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 64.0<\/span>\n\t\t\t<\/td>\n<\/tr>\n
    \n\t\t\t\t 4(2–<\/sup>2Li+<\/sup>)[4]<\/a><\/span><\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 2.02<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 3.59<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 11.69<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 76.8<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 122.6<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 201.8<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 62.2<\/span>\n\t\t\t<\/td>\n<\/tr>\n
    \n\t\t\t\t 5(2–<\/sup>2Li+<\/sup>.H2<\/sub>O)[5]<\/a><\/span><\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 2.03<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 3.39<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 11.82<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 78.4<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 120.9<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 197.4<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 62.5<\/span>\n\t\t\t<\/td>\n<\/tr>\n
    \n\t\t\t\t 6(2–<\/sup>2Li+<\/sup>.2Me2<\/sub>O)[6]<\/a><\/span><\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 2.55<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 3.43<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 10.37<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 86.5<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 113.2<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 182.4<\/span>\n\t\t\t<\/td>\n\n\t\t\t\t 63.5<\/span>\n\t\t\t<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

    \n\tThe most spectacular effect can be seen on the protons on C-11. For the neutral aromatic annulene, they are strongly shielded<\/strong> by a diatropic ring current. For the anti-aromatic di-anion, they are very strongly deshielded<\/strong> by a paratropic ring current, with Δδ 11-12 ppm. Such two-electron reductions (or oxidation) can yield equally spectacular effects on the NMR of other systems as well, as for example extended porphyrins.[7]<\/a><\/span>\n<\/p>\n

    \n\t \n<\/div>\n

    References<\/h2>\n
    1. D. Schmalz, and H. G\u00fcnther, \"1,6\u2010Methano[10]annulene Dianion, a Paratropic 12\u03c0\u2010Electron Dianion with a C<sub>10<\/sub> Perimeter\", Angewandte Chemie International Edition in English<\/i>, vol. 27, pp. 1692-1693, 1988. https:\/\/doi.org\/10.1002\/anie.198816921<\/a>\n\n<\/li>\n
    2. H.S. Rzepa, \"Gaussian Job Archive for C11H10\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.831450<\/a>\n\n<\/li>\n
    3. H.S. Rzepa, \"Gaussian Job Archive for C11H10(2-)\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.832421<\/a>\n\n<\/li>\n
    4. H.S. Rzepa, \"Gaussian Job Archive for C11H10Li2\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.832422<\/a>\n\n<\/li>\n
    5. H.S. Rzepa, \"Gaussian Job Archive for C11H14Li2O2\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.832423<\/a>\n\n<\/li>\n
    6. H.S. Rzepa, \"Gaussian Job Archive for C19H34Li2O4\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.832448<\/a>\n\n<\/li>\n
    7. C.S.M. Allan, and H.S. Rzepa, \"Chiral Aromaticities. AIM and ELF Critical Point and NICS Magnetic Analyses of M\u00f6bius-Type Aromaticity and Homoaromaticity in Lemniscular Annulenes and Hexaphyrins\", The Journal of Organic Chemistry<\/i>, vol. 73, pp. 6615-6622, 2008. https:\/\/doi.org\/10.1021\/jo801022b<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

      The 1H NMR spectrum of an aromatic molecule such as benzene is iconic; one learns that the unusual chemical shift of the protons (~δ 7-8 ppm) is due to their deshielding by a diatropic ring current resulting from the circulation of six aromatic π-electrons following the Hückel 4n+2 rule. But rather less well-known is the […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[4],"tags":[49,1146,1145],"ppma_author":[2661],"class_list":["post-11450","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-chemical-shifts","tag-lithium-metal","tag-unusual-chemical-shift"],"yoast_head":"\nThe NMR spectra of methano[10]annulene and its dianion. The diatropic\/paratropic inversion. - Henry Rzepa's Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=11450\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"The NMR spectra of methano[10]annulene and its dianion. The diatropic\/paratropic inversion. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"The 1H NMR spectrum of an aromatic molecule such as benzene is iconic; one learns that the unusual chemical shift of the protons (~δ 7-8 ppm) is due to their deshielding by a diatropic ring current resulting from the circulation of six aromatic π-electrons following the Hückel 4n+2 rule. 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The best known is the H\u00fcckel 4n+2 rule (n=0,1, etc) for inferring diatropic aromatic ring currents in singlet-state \u03c0-conjugated cyclic molecules\u2021 and a counter 4n rule which infers an antiaromatic paratropic ring current for the system.\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/03\/C2B2-300x212.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":22881,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=22881","url_meta":{"origin":11450,"position":1},"title":"Trimerous pericyclic reactions: what is the effect of changing the electron count by two?","author":"Henry Rzepa","date":"November 2, 2020","format":false,"excerpt":"In an earlier post, I pondered on how the \"arrow pushing\" for the thermal pericyclic reactions of some annulenes (cyclic conjugated hydrocarbons) could be represented in terms of either two separate electrocyclic reactions or of one cycloaddition reaction. Each reaction is governed by selection rules which can be stated in\u2026","rel":"","context":"In "pericyclic"","block_context":{"text":"pericyclic","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=559"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2020\/11\/C2-1024x620.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":1903,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=1903","url_meta":{"origin":11450,"position":2},"title":"Carbobenzene: benzene with a difference","author":"Henry Rzepa","date":"April 16, 2010","format":false,"excerpt":"Some molecules, when you first see them, just intrigue. So it was with carbobenzene, the synthesis of a derivative of which was recently achieved by Remi Chauvin and co-workers (DOI: 10.1002\/chem.200601193). Two additional carbon atoms have been inserted into each of the six C-C bonds in benzene. The structure shows\u2026","rel":"","context":"In "General"","block_context":{"text":"General","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2010\/04\/carbobenzene.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":24503,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=24503","url_meta":{"origin":11450,"position":3},"title":"Molecule of the year 2021: Infinitene.","author":"Henry Rzepa","date":"December 16, 2021","format":false,"excerpt":"The annual \"molecule of the year\" results for 2021 are now available ... and the winner is Infinitene., This is a benzocirculene in the form of a figure eight loop (the infinity symbol), a shape which is also called a lemniscate after the mathematical (2D) function due to Bernoulli. The\u2026","rel":"","context":"In "Chiroptics"","block_context":{"text":"Chiroptics","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2644"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2021\/12\/infinitene.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":9218,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9218","url_meta":{"origin":11450,"position":4},"title":"Aromaticity in the benzidine-like \u03c0-complex formed from PhNHOPh.","author":"Henry Rzepa","date":"January 19, 2013","format":false,"excerpt":"The transient \u03c0-complex formed during the \"[5,5]\" sigmatropic rearrangement of protonated N,O-diphenyl hydroxylamine can be (formally) represented as below, namely the interaction of a six-\u03c0-electron aromatic ring (the phenoxide anion 2) with a\u00a0four-\u03c0-electron phenyl dication-anion pair 1. Can one analyse this interaction in terms of aromaticity? I showed previously that\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"pi-QTAIM","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/pi-QTAIM.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":8398,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8398","url_meta":{"origin":11450,"position":5},"title":"Di-imide reduction with a twist: A M\u00f6bius version.","author":"Henry Rzepa","date":"November 26, 2012","format":false,"excerpt":"I was intrigued by one aspect of the calculated transition state for di-imide reduction of an alkene; the calculated NMR shieldings indicated an diatropic ring current at the centre of the ring, but very deshielded shifts for the hydrogen atoms being transferred. This indicated, like most thermal pericyclic reactions, an\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/11\/GaussViewScreenSnapz004.jpg?resize=350%2C200","width":350,"height":200},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/11450","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=11450"}],"version-history":[{"count":39,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/11450\/revisions"}],"predecessor-version":[{"id":15815,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/11450\/revisions\/15815"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=11450"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=11450"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=11450"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=11450"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}