{"id":984,"date":"2009-10-03T16:28:27","date_gmt":"2009-10-03T15:28:27","guid":{"rendered":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984"},"modified":"2009-10-05T21:36:13","modified_gmt":"2009-10-05T20:36:13","slug":"monovalent-helium","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984","title":{"rendered":"Uncompressed Monovalent Helium"},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"984\">\n<p>Quite a few threads have developed in this series of posts, and following each leads in rather different directions. In <a href=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=878\" target=\"references\">this previous post<\/a> the comment was made that coordinating a carbon dication to the face of a cyclopentadienyl anion resulted in a monocation which had a remarkably high proton affinity. So it is a simple progression to ask whether these systems may in turn harbour a large affinity for binding not so much a  H<sup>+<\/sup> as the next homologue He<sup>2+<\/sup>?<\/p>\n<div id=\"attachment_988\" style=\"width: 99px\" class=\"wp-caption aligncenter\"><img loading=\"lazy\" decoding=\"async\" aria-describedby=\"caption-attachment-988\" class=\"size-full wp-image-988\" title=\"C4-He\" src=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4-He.jpg\" alt=\"Inventing the  Helium bond\" width=\"89\" height=\"168\" \/><p id=\"caption-attachment-988\" class=\"wp-caption-text\">Inventing the  Helium bond<\/p><\/div>\n<p>This possibility is explored with the series X=Be, B, C (tetramethyl substituted, resulting in neutral,  +1 and +2 systems overall). The first two emerge as stable in terms of having all positive force constants for  C<sub>4v<\/sub> symmetry; the last emerges as a transition state and is not discussed further. The specific system X=B has a B-He bond length of 1.317\u00c5\/B3LYP\/6-311G(d,p), 1.305\u00c5\/B3LYP\/Def2-QZVPP\u00a0and 1.290\u00c5\/double-hybrid RI-B2GP-B2PLYP\/TZVPP, which does seem as if it might be typical of a single bond between these two elements. The \u03c1(r)<sub>B-He<\/sub> AIM value (B3LYP\/6-311G(d,p) is 0.069 au, and \u03bd<sub>B-He<\/sub> of 713 cm<sup>-1<\/sup> (727 for Def2-QZVPP basis) makes it about one third the strength of a C-H bond. The disynaptic basin for the B-He region integrates to 1.99 electrons, whilst the four B-C basins correspond to 1.22 electrons each.<\/p>\n<table border=\"1\">\n<tbody>\n<tr>\n<td>X<\/td>\n<td>Charge<\/td>\n<td>\u03c1(r) X-He<\/td>\n<td>C-B ELF<br \/>\nintegration<\/td>\n<td>\u03bd<sub>X-He<\/sub>, cm<sup>-1<\/sup><\/td>\n<td>Repository<\/td>\n<\/tr>\n<tr>\n<td>Be<\/td>\n<td>0<\/td>\n<td>0.031<\/td>\n<td>1.10<\/td>\n<td>484<\/td>\n<td><a href=\"http:\/\/hdl.handle.net\/10042\/to-2443\" target=\"references\">10042\/to-2443<\/a><\/td>\n<\/tr>\n<tr>\n<td>B<\/td>\n<td>1<\/td>\n<td>0.069<\/td>\n<td>1.22<\/td>\n<td>713<\/td>\n<td><a href=\"http:\/\/hdl.handle.net\/10042\/to-2444\" target=\"references\">10042\/to-2444<\/a><\/p>\n<p><\/a><a href=\"http:\/\/hdl.handle.net\/10042\/to-2446\" target=\"references\">10042\/to-2446<\/a><\/p>\n<p><a href=\"http:\/\/hdl.handle.net\/10042\/to-2453\" target=\"references\">10042\/to-2453<\/a><\/td>\n<\/tr>\n<tr>\n<td>C<\/td>\n<td>2<\/td>\n<td>0.026<\/td>\n<td>&#8211;<\/td>\n<td>136<\/td>\n<td><a href=\"http:\/\/hdl.handle.net\/10042\/to-2445\" target=\"references\">10042\/to-2445<\/a><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<table border=\"0\">\n<tbody>\n<tr>\n<td><div id=\"attachment_995\" style=\"width: 212px\" class=\"wp-caption aligncenter\"><img loading=\"lazy\" decoding=\"async\" aria-describedby=\"caption-attachment-995\" class=\"size-full wp-image-995\" title=\"c4-BHe-aim\" onclick=\"jmolInitialize('..\/Jmol\/');jmolSetAppletColor('white');jmolApplet([450,450],'load wp-content\/uploads\/2009\/10\/C4-BHe-elf.mol; frame 1; zoom 100;spin 3;');\" src=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/c4-BHe-aim1.jpg\" alt=\"AIM for X=B-He\" width=\"202\" height=\"172\" \/><p id=\"caption-attachment-995\" class=\"wp-caption-text\">AIM for X=B-He. Click for  3D<\/p><\/div><\/td>\n<td><div id=\"attachment_998\" style=\"width: 220px\" class=\"wp-caption aligncenter\"><img loading=\"lazy\" decoding=\"async\" aria-describedby=\"caption-attachment-998\" class=\"size-full wp-image-998\" title=\"c4-BHe-vib\" onclick=\"jmolInitialize('..\/Jmol\/');jmolSetAppletColor('white');jmolApplet([450,450],'load wp-content\/uploads\/2009\/10\/C4-BHe.xyz; frame 1; zoom 100;connect (atomno=21) (atomno=5) PARTIAL;vectors  on;vectors 4;vectors scale -5.0; color vectors green; vibration 10;animation mode loop;');\" src=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/c4-BHe-vib.jpg\" alt=\"B-He vibrational stretching mode\" width=\"210\" height=\"172\" \/><p id=\"caption-attachment-998\" class=\"wp-caption-text\">B-He stretching mode. Click to vibrate<\/p><\/div><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<p>We can conclude that for  X=B, this species exhibits not only a pentavalent boron atom, but a monovalent helium atom. The latter bond may indeed be amongst the strongest ever proposed for this element in a ground state, and indeed perhaps is even viable as a solid crystalline compound rather than merely existing in the gas phase. The Cambridge crystal database contains no entries for\u00a0He or Ne, not even as an encapsulated clathrate (although crystal structures of such complexes for Kr and Ar are known). Theoretical studies of the rare gases in endohedral fullerene-like cages (DOI:\u00a0<a href=\"http:\/\/dx.doi.org\/10.1002\/chem.200700467\" target=\"references\">10.1002\/chem.200801399<\/a>) predict that under these compressed circumstances <em>e.g.<\/em> two helium atoms can approach each other to 1.265\u00c5 or less (see also  DOI: <a href=\"http:\/\/dx.doi.org\/10.1002\/chem.200700467\" target=\"references\">10.1002\/chem.200700467<\/a>) but these close approaches were not considered to be <em>chemical bonds<\/em> as we think of them. Perhaps Merino, Frenking, Krapp and co&#8217;s search for the chemistry of helium (they had found it earlier in the gas phase excited states of their molecules, DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/ja00254a005\" target=\"references\">10.1021\/ja00254a005<\/a>)\u00a0might be realised for the ground state of the system described here.<\/p>\n<!-- kcite active, but no citations found -->\n<\/div> <!-- kcite-section 984 -->","protected":false},"excerpt":{"rendered":"<p>Quite a few threads have developed in this series of posts, and following each leads in rather different directions. In this previous post the comment was made that coordinating a carbon dication to the face of a cyclopentadienyl anion resulted in a monocation which had a remarkably high proton affinity. So it is a simple [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_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},"jetpack_post_was_ever_published":false},"categories":[7,4],"tags":[10,8,144,146,12,11,145,2649,9,2648,147],"ppma_author":[2661],"class_list":["post-984","post","type-post","status-publish","format-standard","hentry","category-hypervalency","category-interesting-chemistry","tag-aim","tag-bonding","tag-cambridge","tag-chemical-bonds","tag-double-hybrid","tag-elf","tag-gas-phase","tag-hypervalency","tag-hypervalent","tag-interesting-chemistry","tag-krapp-and-co"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.6 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Uncompressed Monovalent Helium - 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=984\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Uncompressed Monovalent Helium - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"Quite a few threads have developed in this series of posts, and following each leads in rather different directions. 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In this previous post the comment was made that coordinating a carbon dication to the face of a cyclopentadienyl anion resulted in a monocation which had a remarkably high proton affinity. So it is a simple [&hellip;]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984","og_site_name":"Henry Rzepa&#039;s Blog","article_published_time":"2009-10-03T15:28:27+00:00","article_modified_time":"2009-10-05T20:36:13+00:00","og_image":[{"url":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4-He.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=984#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"Uncompressed Monovalent Helium","datePublished":"2009-10-03T15:28:27+00:00","dateModified":"2009-10-05T20:36:13+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984"},"wordCount":466,"commentCount":1,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4-He.jpg","keywords":["AIM","bonding","Cambridge","chemical bonds","double-hybrid","ELF","gas phase","Hypervalency","hypervalent","Interesting chemistry","Krapp and co"],"articleSection":["Hypervalency","Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984","name":"Uncompressed Monovalent Helium - 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The latter is defined not so much by expanding the total valence shell of electrons surrounding the hypervalent\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":"YOCVIV: Crystal structure of hexacoordinate boron","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/BBr.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":19383,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19383","url_meta":{"origin":984,"position":1},"title":"Hypervalent  Helium &#8211; not!","author":"Henry Rzepa","date":"February 16, 2018","format":false,"excerpt":"Last year, this article attracted a lot of attention as the first example of molecular helium in the form of Na2He. In fact, the helium in this species has a calculated\u2021 bond index of only 0.15 and it is better classified as a sodium electride with the ionisation induced by\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":"","width":0,"height":0},"classes":[]},{"id":961,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961","url_meta":{"origin":984,"position":2},"title":"Pentavalent nitrogen and boron","author":"Henry Rzepa","date":"October 3, 2009","format":false,"excerpt":"The previous posts have seen how a molecule containing a hypervalent carbon atom can be designed by making a series of logical chemical connections. Another logical step is to investigate whether the adjacent atoms in the periodic table may exhibit similar effects (C2+ \u2261 B+ \u2261 N3+ \u2261 Be \u2261\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":"Pentavalency across a series","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":878,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=878","url_meta":{"origin":984,"position":3},"title":"It&#8217;s Hexa-coordinate carbon Spock &#8211; but not as we know it!","author":"Henry Rzepa","date":"October 2, 2009","format":false,"excerpt":"Science is about making connections. And these can often be made between the most unlikely concepts. Thus in the posts I have made about pentavalent carbon, one can identify a series of conceptual connections. The\u00a0first, by Matthias\u00a0Bickelhaupt and co, resulted in the suggestion of a possible frozen\u00a0SN2 transition state. They\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":"The HOMO orbital","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/09\/C5-homo1.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":19279,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19279","url_meta":{"origin":984,"position":4},"title":"Can any hypervalence in diazomethanes be amplified?","author":"Henry Rzepa","date":"December 23, 2017","format":false,"excerpt":"In the previous post, I referred to a recently published review on hypervalency which introduced a very simple way (the\u00a0valence electron equivalent \u03b3)\u00a0of quantifying the effect.\u00a0Diazomethane was cited as one example of a small molecule exhibiting hypervalency (on nitrogen) by this measure. Here I explore the effect of substituting diazomethane\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":"","width":0,"height":0},"classes":[]},{"id":936,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=936","url_meta":{"origin":984,"position":5},"title":"Full circle with carbon hypervalencies","author":"Henry Rzepa","date":"October 2, 2009","format":false,"excerpt":"The previous post talked about making links or connections. And part of the purpose for presenting this chemistry as a blog is to expose how these connections are made, or or less as it happens in real time (and\u00a0not the chronologically sanitized version of discovery that most research papers are).\u00a0So\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":"C4-symmetric pentavalent carbon","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/c4.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\/984","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=984"}],"version-history":[{"count":0,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/984\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=984"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=984"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=984"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=984"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}