{"id":10641,"date":"2013-05-24T10:54:39","date_gmt":"2013-05-24T09:54:39","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=10641"},"modified":"2014-01-17T07:46:36","modified_gmt":"2014-01-17T07:46:36","slug":"how-should-one-represent-the-anion-of-tosmic","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641","title":{"rendered":"How should one represent the anion of TosMIC?"},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"10641\">\n<p>The title of this post comes from a comment posted by <a href=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=10518&amp;cpage=1#comment-52740\" target=\"_blank\">Ryan<\/a>, who asks about isocyanide\u2019s role (in the form of the anion of tosyl isocyanide, or TosMIC) in two named reactions, <a href=\"http:\/\/en.wikipedia.org\/wiki\/Van_Leusen_reaction\" target=\"_blank\">Van Leusen<\/a> and Ugi FCR.\u00a0 &#8220;In Van Leusen, it (the isocyanide) acts as an electrophile: however, in Ugi, it acts as a nucleophile&#8221;. Here are some valence bond forms for this species;<\/p>\n<p><img decoding=\"async\" class=\"aligncenter size-full wp-image-10642\" alt=\"tosmic\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/tosmic.svg\" width=\"440\" \/><\/p>\n<p>Thus we see representation<strong>\u00a03<\/strong> as a vinyl carbene, and because the carbon is isoelectronic with a carbocation, it could be regarded as an electrophile (with donation into an empty p-orbital). With <strong>2<\/strong>, we see that that this anion is actually isoelectronic with diazomethane <strong>4<\/strong>, a species that can act as a <a href=\"http:\/\/en.wikipedia.org\/wiki\/Diazoalkane_1,3-dipolar_cycloaddition\" target=\"_blank\">1,3-dipole in cycloaddition reactions<\/a>. Form <strong>2<\/strong> is also of interest in another context; the terminal carbon can be regarded as using none of its four valence electrons for bonding (having them all in two lone pairs). Frenking has described such species as divalent C(0), or carbones<span id=\"cite_ITEM-10641-0\" name=\"citation\"><a href=\"#ITEM-10641-0\">[1]<\/a><\/span>.\u00a0 With <strong>1<\/strong>, we see isoelectronic analogy to the acetylide anion, where the terminal carbon is nucleophilic. So three different personalities, and as is often the case, such chameleon character can also reflect in the reactions.<\/p>\n<p>Because <strong>1-3<\/strong> effectively differ in how the two lone pairs are distributed, it is useful to analyse the actual character using a method which can locate and count them. So here is an ELF analysis<span id=\"cite_ITEM-10641-1\" name=\"citation\"><a href=\"#ITEM-10641-1\">[2]<\/a><\/span> which can provide the centroids of electron basins together with the required integration.<\/p>\n<div id=\"attachment_10644\" style=\"width: 422px\" class=\"wp-caption aligncenter\"><img loading=\"lazy\" decoding=\"async\" aria-describedby=\"caption-attachment-10644\" class=\" wp-image-10644  \" onclick=\"jmolInitialize('..\/Jmol\/','JmolAppletSigned.jar');jmolSetAppletColor('white');jmolApplet([450,450],'load wp-content\/uploads\/2013\/05\/tosmic_bas.mol;');\" alt=\"Click for  3D\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/tosmic.jpeg\" width=\"412\" height=\"242\" \/><p id=\"caption-attachment-10644\" class=\"wp-caption-text\">Click for 3D<\/p><\/div>\n<p>This reveals <strong>1<\/strong> as the closest match. Thus the terminal carbon has two disynaptic basins and one monosynaptic basin corresponding to 2.71 electrons giving a total valence electron count of 8.08 (which excludes <strong>3<\/strong>), rather closer to acetylide <strong>1<\/strong> than to the carbone <strong>2<\/strong>. Another lone pair is located on the first carbon (2.17) which again matches structure <strong>1<\/strong>, and that carbon is indeed strongly pyramidal, and presumably also strongly nucleophilic. A similar conclusion emerges from NBO analysis, which reveals two\u00a0\u03c0-type NBOs and one terminal lone pair NBO on the isocyanide group, indicating the acetylide form.<\/p>\n<p>I will deal with whether the reactions of this species reflect the nucleophilic or electrophilic character of the isocyanide group in a separate post.<\/p>\n<h2>References<\/h2>\n    <ol class=\"kcite-bibliography csl-bib-body\"><li id=\"ITEM-10641-1\">H.S. Rzepa, \"Gaussian Job Archive for C4H6NO3S(1-)\", 2013. <a href=\"https:\/\/doi.org\/10.6084\/m9.figshare.706756\">https:\/\/doi.org\/10.6084\/m9.figshare.706756<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> <!-- kcite-section 10641 -->","protected":false},"excerpt":{"rendered":"<p>The title of this post comes from a comment posted by Ryan, who asks about isocyanide\u2019s role (in the form of the anion of tosyl isocyanide, or TosMIC) in two named reactions, Van Leusen and Ugi FCR.\u00a0 &#8220;In Van Leusen, it (the isocyanide) acts as an electrophile: however, in Ugi, it acts as a nucleophile&#8221;. [&hellip;]<\/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":[1068,1069],"ppma_author":[2661],"class_list":["post-10641","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-ugi","tag-van-leusen"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.5 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>How should one represent the anion of TosMIC? - Henry Rzepa&#039;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=10641\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"How should one represent the anion of TosMIC? - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"The title of this post comes from a comment posted by Ryan, who asks about isocyanide\u2019s role (in the form of the anion of tosyl isocyanide, or TosMIC) in two named reactions, Van Leusen and Ugi FCR.\u00a0 &#8220;In Van Leusen, it (the isocyanide) acts as an electrophile: however, in Ugi, it acts as a nucleophile&#8221;. 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[&hellip;]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641","og_site_name":"Henry Rzepa&#039;s Blog","article_published_time":"2013-05-24T09:54:39+00:00","article_modified_time":"2014-01-17T07:46:36+00:00","og_image":[{"url":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/tosmic.svg","type":"","width":"","height":""}],"author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"2 minutes"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"How should one represent the anion of TosMIC?","datePublished":"2013-05-24T09:54:39+00:00","dateModified":"2014-01-17T07:46:36+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641"},"wordCount":379,"commentCount":2,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/tosmic.svg","keywords":["Ugi","Van Leusen"],"articleSection":["Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10641","name":"How should one represent the anion of TosMIC? 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The Wikipedia article (recently updated by myself) shows nucleophilic attack by an oxy-anion on the\u2026","rel":"","context":"In \"low energy\"","block_context":{"text":"low energy","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=low-energy"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":27944,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=27944","url_meta":{"origin":10641,"position":1},"title":"A one-electron bond in methyl-\u03bb1-borane.","author":"Henry Rzepa","date":"October 9, 2024","format":false,"excerpt":"In exploring one-electron carbon-carbon bonds, I had noted previously that both hexafluoroethane and ethane itself could each lose an electron to produce such species. A discussion developed in which a molecule isoelectronic with ethane radical cation, namely the methyl-\u03bb1-borane radical (H3B-CH3) was proposed by Jacob. The optimised structure at the\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":12895,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12895","url_meta":{"origin":10641,"position":2},"title":"Computationally directed synthesis:  2,3-dimethyl-2-butene + NO(+).","author":"Henry Rzepa","date":"September 6, 2014","format":false,"excerpt":"In the previous posts, I explored reactions which can be flipped between two potential (stereochemical) outcomes. This triggered a memory from Alex, who pointed out this article from 1999 in which the nitrosonium cation as an electrophile can have two outcomes A or B when interacting with the electron-rich 2,3-dimethyl-2-butene.\u2026","rel":"","context":"In &quot;pericyclic&quot;","block_context":{"text":"pericyclic","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=559"},"img":{"alt_text":"NOa","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2014\/09\/NOa.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":25486,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25486","url_meta":{"origin":10641,"position":3},"title":"Octafluorocubane radical anion &#8211;  where does the extra electron sit?","author":"Henry Rzepa","date":"August 29, 2022","format":false,"excerpt":"Derek Lowe reports the story that the recently synthesized octafluorocubane can absorb one electron to form a radical anion - an electron in a cube. So I thought it would be fun to compute exactly where that electron sits! A\u00a0\u03c9B97XD\/Def2-TZVPPD\/SCRF=chloroform\u00a0calculation (DOI: 10.14469\/hpc\/11090) is carried out on the neutral system (optimizing\u2026","rel":"","context":"With 10 comments","block_context":{"text":"With 10 comments","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25486#comments"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/perfluorotetrahedrane-anion_den_sub.png?resize=350%2C200&ssl=1","width":350,"height":200,"srcset":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/perfluorotetrahedrane-anion_den_sub.png?resize=350%2C200&ssl=1 1x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/perfluorotetrahedrane-anion_den_sub.png?resize=525%2C300&ssl=1 1.5x"},"classes":[]},{"id":18806,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18806","url_meta":{"origin":10641,"position":4},"title":"The di-anion of dilithium (not the Star Trek variety): Another &#8220;Hyper-bond&#8221;?","author":"Henry Rzepa","date":"September 16, 2017","format":false,"excerpt":"Early in 2011, I wrote about how the diatomic molecule Be2 might be persuaded to improve upon its normal unbound state (bond order\u00a0~zero) by a double electronic excitation to a strongly bound species. I yesterday updated this post with further suggestions and one of these inspired this follow-up. The standard\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","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\/2011\/01\/Be2b.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":21925,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=21925","url_meta":{"origin":10641,"position":5},"title":"The singlet and open shell higher-spin states of [4], [6] and [8]-annulenes and their Kekul\u00e9 vibrational modes","author":"Henry Rzepa","date":"March 11, 2020","format":false,"excerpt":"In 2001, Shaik and co-workers published the first of several famous review articles on the topic\u00a0A Different Story of \u03c0-Delocalization. The Distortivity of \u03c0-Electrons and Its Chemical Manifestations. The main premise was that the delocalized \u03c0-electronic component of benzene is unstable toward a localizing distortion and is at the same\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","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\/2020\/03\/CBD-Eu.gif?resize=350%2C200&ssl=1","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\/10641","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=10641"}],"version-history":[{"count":8,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/10641\/revisions"}],"predecessor-version":[{"id":11945,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/10641\/revisions\/11945"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=10641"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=10641"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=10641"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=10641"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}