{"id":3977,"date":"2011-04-29T07:26:20","date_gmt":"2011-04-29T07:26:20","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=3977"},"modified":"2011-04-29T07:37:59","modified_gmt":"2011-04-29T07:37:59","slug":"nobelocene-a-hypothetical-32-electron-shell-molecule","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3977","title":{"rendered":"Nobelocene: a (hypothetical) 32-electron shell molecule?"},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"3977\">\n<p>The <a href=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=3956\" target=\"_blank\">two previous posts<\/a> have explored one of the oldest bonding rules (pre-dating quantum mechanics), which postulated that filled valence shells in atoms forming molecules follow the magic numbers 2, 8, 18 and 32. Of the 59,025,533 molecules documented at the instant I write this post, only <a href=\"http:\/\/dx.doi.org\/10.1002\/anie.200604198\" target=\"_blank\">one example<\/a> is claimed for the 32-electron class. Here I suggest another, <strong>Nobelocene<\/strong> (one which given the radioactive instability of nobelium, is unlikely to be ever confirmed experimentally!)<\/p>\n<p>Nobelium has the electronic configuration [Rn].5f<sup>14<\/sup>.7s<sup>2 <\/sup>, which means the 6d and\u00a07p shells are still empty. Filling these would take 10+6 electrons, or four more\u00a0electrons (<strong>20<\/strong>) if one starts from No<sup>4+<\/sup>, resulting in a complete 32-electron filled shell for the Nobelium. These twenty electrons could be provided by two cyclo-octatetraenyl (COT) dianion ligands. Nobelium, with its nuclear charge of +102, has highly relativistic inner-shell electrons, and so special techniques must be used to model this. Here I have used a SARC a<em>ll electron relativistically contracted<\/em> basis set (DOI:\u00a0<a href=\"http:\/\/dx.doi.org\/10.1021\/ct100736b\" target=\"_blank\">10.1021\/ct100736b<\/a>), to be used with the\u00a0<em>Douglas\u2212Kroll\u2212Hess scalar relativistic Hamiltonian (<\/em>for details, <a href=\"http:\/\/hdl.handle.net\/10042\/to-8401\" target=\"_blank\">see here<\/a>). The QTAIM analysis is shown below (quite a spider&#8217;s web):<\/p>\n<p><div id=\"attachment_3979\" style=\"width: 230px\" class=\"wp-caption aligncenter\"><img loading=\"lazy\" decoding=\"async\" aria-describedby=\"caption-attachment-3979\" class=\"size-full wp-image-3979\" title=\"nobelocene_aim\" onclick=\"jmolInitialize('..\/Jmol\/');jmolSetAppletColor('white');jmolApplet([450,450],'load wp-content\/uploads\/2011\/04\/No-aim.mol2;spin 3;');\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_aim.jpg\" alt=\"\" width=\"220\" height=\"216\" srcset=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_aim.jpg 439w, https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_aim-300x295.jpg 300w\" sizes=\"auto, (max-width: 220px) 100vw, 220px\" \/><p id=\"caption-attachment-3979\" class=\"wp-caption-text\">Nobelocene. AIM analysis. Click for 3D.<\/p><\/div>There are 16 bond critical points located along the lines of each No..C, with \u03c1(r) 0.03. This is a very low value indeed for a covalent bond, being of the same order as strong hydrogen bonds, and so should be classed as an interaction rather than a bond. ELF basins cannot normally be located for hydrogen bonds, and neither can they here. Nobelocene in this regard is pretty boring, being almost entirely ionic.<\/p>\n<p><div id=\"attachment_3981\" style=\"width: 328px\" class=\"wp-caption aligncenter\"><img loading=\"lazy\" decoding=\"async\" aria-describedby=\"caption-attachment-3981\" class=\"size-full wp-image-3981\" title=\"nobelocene_elf\" onclick=\"jmolInitialize('..\/Jmol\/');jmolSetAppletColor('white');jmolApplet([450,450],'load wp-content\/uploads\/2011\/04\/Nob_bas.mol2;spin 3;');\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_elf.jpg\" alt=\"\" width=\"318\" height=\"308\" srcset=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_elf.jpg 636w, https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_elf-300x290.jpg 300w\" sizes=\"auto, (max-width: 318px) 100vw, 318px\" \/><p id=\"caption-attachment-3981\" class=\"wp-caption-text\">ELF analysis for Nobelocene.<\/p><\/div>Rather more interesting are the molecular orbitals. The most stable \u03c0-type is shown below. Many of the orbitals show the Nobelium atomic orbitals non-interacting with the ligand, probably because the relativistic contraction renders them inert to mixing, in a manner which is often used to explain the inert nature of e.g. the Pb 6s<sup>2<\/sup> electrons in divalent lead.<\/p>\n<div id=\"attachment_3983\" style=\"width: 169px\" class=\"wp-caption aligncenter\"><img loading=\"lazy\" decoding=\"async\" aria-describedby=\"caption-attachment-3983\" class=\"size-full wp-image-3983\" title=\"nobelocene_mo84\" onclick=\"jmolInitialize('..\/Jmol\/');jmolSetAppletColor('white');jmolApplet([450,450],'load wp-content\/uploads\/2011\/04\/No_mo84_0.02.jvxl;isosurface &quot;&quot; translucent;zoom 100;spin 3;');\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_mo84.jpg\" alt=\"\" width=\"159\" height=\"136\" srcset=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_mo84.jpg 318w, https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_mo84-300x256.jpg 300w\" sizes=\"auto, (max-width: 159px) 100vw, 159px\" \/><p id=\"caption-attachment-3983\" class=\"wp-caption-text\">Molecular orbital for nobelocene. Click for 3D.<\/p><\/div>\n<!-- kcite active, but no citations found -->\n<\/div> <!-- kcite-section 3977 -->","protected":false},"excerpt":{"rendered":"<p>The two previous posts have explored one of the oldest bonding rules (pre-dating quantum mechanics), which postulated that filled valence shells in atoms forming molecules follow the magic numbers 2, 8, 18 and 32. Of the 59,025,533 molecules documented at the instant I write this post, only one example is claimed for the 32-electron class. [&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":false,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[4],"tags":[519,74],"ppma_author":[2661],"class_list":["post-3977","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-hess","tag-pence"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.5 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Nobelocene: a (hypothetical) 32-electron shell molecule? - 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=3977\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Nobelocene: a (hypothetical) 32-electron shell molecule? - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"The two previous posts have explored one of the oldest bonding rules (pre-dating quantum mechanics), which postulated that filled valence shells in atoms forming molecules follow the magic numbers 2, 8, 18 and 32. Of the 59,025,533 molecules documented at the instant I write this post, only one example is claimed for the 32-electron class. 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Of the 59,025,533 molecules documented at the instant I write this post, only one example is claimed for the 32-electron class. [&hellip;]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3977","og_site_name":"Henry Rzepa&#039;s Blog","article_published_time":"2011-04-29T07:26:20+00:00","article_modified_time":"2011-04-29T07:37:59+00:00","og_image":[{"url":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_aim.jpg","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=3977#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3977"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"Nobelocene: a (hypothetical) 32-electron shell molecule?","datePublished":"2011-04-29T07:26:20+00:00","dateModified":"2011-04-29T07:37:59+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3977"},"wordCount":364,"commentCount":4,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3977#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/nobelocene_aim.jpg","keywords":["Hess","pence"],"articleSection":["Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3977#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3977","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3977","name":"Nobelocene: a (hypothetical) 32-electron shell molecule? 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The first two dominate organic chemistry of course, whilst\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.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/04\/beryllocene-elf.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":14272,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=14272","url_meta":{"origin":3977,"position":1},"title":"Electrides (aka solvated electrons).","author":"Henry Rzepa","date":"July 8, 2015","format":false,"excerpt":"Peter Edwards has just given the 2015 Hofmann lecture here at Imperial on the topic of solvated electrons. An organic chemist knows this species as \"e-\" and it occurs in ionic compounds known as electrides; chloride = the negative anion of a chlorine atom, hence electride = the negative anion\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":23588,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=23588","url_meta":{"origin":3977,"position":2},"title":"Two new reality-based suggestions for molecules with a metal M\u2a78C quadruple bond.","author":"Henry Rzepa","date":"May 8, 2021","format":false,"excerpt":"Following from much discussion over the last decade about the nature of C2, a diatomic molecule which some have suggested sustains a quadruple bond between the two carbon atoms, new ideas are now appearing for molecules in which such a bond may also exist between carbon and a transition metal\u2026","rel":"","context":"In &quot;crystal_structure_mining&quot;","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2021\/05\/Screenshot-702-300x63.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":1691,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=1691","url_meta":{"origin":3977,"position":3},"title":"Quintuple bonds","author":"Henry Rzepa","date":"February 16, 2010","format":false,"excerpt":"Climbers scale Mt. Everest, because its there, and chemists have their own version of this. Ever since G. N. Lewis introduced the concept of the electron-pair bond in 1916, the idea of a bond as having a formal bond-order has been seen as a useful way of thinking about molecules.\u2026","rel":"","context":"In &quot;Hypervalency&quot;","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2010\/02\/Cr.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":4340,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=4340","url_meta":{"origin":3977,"position":4},"title":"Less is more: the dyotropic rearrangement of ethane","author":"Henry Rzepa","date":"June 11, 2011","format":false,"excerpt":"In a time when large (molecules) are considered beautiful (or the corollary that beauty must be big), it is good to reflect that small molecules may teach us something as well. Take ethane. Is there anything left which has not been said about it already? Well, consider the reaction below,\u2026","rel":"","context":"In \"animation\"","block_context":{"text":"animation","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=animation"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/06\/c2h6.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":8048,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8048","url_meta":{"origin":3977,"position":5},"title":"Trimethylenemethane Ruthenium benzene","author":"Henry Rzepa","date":"October 17, 2012","format":false,"excerpt":"Every once in a while, one encounters a molecule which instantly makes an interesting point. Thus Ruthenium is ten electrons short of completing an 18-electron shell, and it can form a complex with benzene on one face and a ligand known as trimethylenemethane on the other. This four-carbon molecule has\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.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/10\/JODLIX.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\/3977","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=3977"}],"version-history":[{"count":0,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/3977\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=3977"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=3977"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=3977"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=3977"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}