{"id":961,"date":"2009-10-03T09:42:06","date_gmt":"2009-10-03T08:42:06","guid":{"rendered":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961"},"modified":"2009-10-03T17:03:03","modified_gmt":"2009-10-03T16:03:03","slug":"pentavalent-nitrogen-and-boron","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961","title":{"rendered":"Pentavalent nitrogen and boron"},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"961\">\n<p>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 (C<sup>2+<\/sup> \u2261 B<sup>+<\/sup> \u2261 N<sup>3+<\/sup> \u2261 Be \u2261 O<sup>4+<\/sup>). So here are reported some results (B3LYP\/6-311G(d,p) ) for boron, beryllium and nitrogen, for the general tetramethyl substituted system shown below<\/p>\n<div id=\"attachment_964\" style=\"width: 88px\" class=\"wp-caption aligncenter\"><img loading=\"lazy\" decoding=\"async\" aria-describedby=\"caption-attachment-964\" class=\"size-full wp-image-964\" title=\"C4\" src=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4.jpg\" alt=\"Pentavalency across a series\" width=\"78\" height=\"170\" \/><p id=\"caption-attachment-964\" class=\"wp-caption-text\">Pentavalency across a series<\/p><\/div>\n<table border=\"1\">\n<tbody>\n<tr>\n<td>X<\/td>\n<td>Charge<\/td>\n<td>X-C length, \u00c5<\/td>\n<td>\u03c1(r) C-X<\/td>\n<td>ELF integration<\/td>\n<td>\u03bd-Trampoline, cm<sup>-1<\/sup><\/td>\n<td>\u03bd X-H, cm<sup>-1<\/sup><\/td>\n<td>Repository<\/td>\n<\/tr>\n<tr>\n<td>N<\/td>\n<td>2<\/td>\n<td>1.616<\/td>\n<td>.172<\/td>\n<td>1.14<\/td>\n<td>883<\/td>\n<td>3417<\/td>\n<td><a href=\"http:\/\/hdl.handle.net\/10042\/to-2439\" target=\"references\">10042\/to-2439<\/a><\/td>\n<\/tr>\n<tr>\n<td>C<\/td>\n<td>1<\/td>\n<td>1.580<\/td>\n<td>.195<\/td>\n<td>1.10<\/td>\n<td>970<\/td>\n<td>3291<\/td>\n<td><a href=\"http:\/\/hdl.handle.net\/10042\/to-2438\" target=\"references\">10042\/to-2438<\/a><\/td>\n<\/tr>\n<tr>\n<td>B<\/td>\n<td>0<\/td>\n<td>1.649<\/td>\n<td>.136<\/td>\n<td>1.06<\/td>\n<td>949<\/td>\n<td>2746<\/td>\n<td><a href=\"http:\/\/hdl.handle.net\/10042\/to-2440\" target=\"references\">10042\/to-2440<\/a><\/td>\n<\/tr>\n<tr>\n<td>Be<\/td>\n<td>-1<\/td>\n<td>1.817<\/td>\n<td>.064<\/td>\n<td>0.98<\/td>\n<td>797<\/td>\n<td>1887<\/td>\n<td><a href=\"http:\/\/hdl.handle.net\/10042\/to-2441\" target=\"references\">10042\/to-2441<\/a><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<p>The systems H, C and B are stable in the sense that the C<sub>4v<\/sub>-symmetric calculated geometry has only positive calculated force constants (Be has a small negative frequency).  All show bond critical points in the \u00a0X-C region (although these bonds are clearly \u00a0bent) and X-H region, and significant integrations for the X-C disynaptic basins in the \u00a0ELF analysis. The boron analogue is also of interest as being a neutral rather than a charged molecule, and therefore may be a worthy target for synthetic effort.<\/p>\n<!-- kcite active, but no citations found -->\n<\/div> <!-- kcite-section 961 -->","protected":false},"excerpt":{"rendered":"<p>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 O4+). So here are reported [&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_feature_clip_id":0,"_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":[2649,2648,143],"ppma_author":[2661],"class_list":["post-961","post","type-post","status-publish","format-standard","hentry","category-hypervalency","category-interesting-chemistry","tag-hypervalency","tag-interesting-chemistry","tag-logical-chemical-connections"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.9 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Pentavalent nitrogen and boron - 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=961\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Pentavalent nitrogen and boron - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"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 O4+). So here are reported [&hellip;]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"article:published_time\" content=\"2009-10-03T08:42:06+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2009-10-03T16:03:03+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4.jpg\" \/>\n<meta name=\"author\" content=\"Henry Rzepa\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Henry Rzepa\" \/>\n\t<meta name=\"twitter:label2\" content=\"Estimated reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"1 minute\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Pentavalent nitrogen and boron - Henry Rzepa&#039;s Blog","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961","og_locale":"en_GB","og_type":"article","og_title":"Pentavalent nitrogen and boron - Henry Rzepa&#039;s Blog","og_description":"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 O4+). So here are reported [&hellip;]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961","og_site_name":"Henry Rzepa&#039;s Blog","article_published_time":"2009-10-03T08:42:06+00:00","article_modified_time":"2009-10-03T16:03:03+00:00","og_image":[{"url":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4.jpg","type":"","width":"","height":""}],"author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"1 minute"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"Pentavalent nitrogen and boron","datePublished":"2009-10-03T08:42:06+00:00","dateModified":"2009-10-03T16:03:03+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961"},"wordCount":195,"commentCount":0,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4.jpg","keywords":["Hypervalency","Interesting chemistry","logical chemical connections"],"articleSection":["Hypervalency","Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961","name":"Pentavalent nitrogen and boron - Henry Rzepa&#039;s Blog","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#website"},"primaryImageOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961#primaryimage"},"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4.jpg","datePublished":"2009-10-03T08:42:06+00:00","dateModified":"2009-10-03T16:03:03+00:00","author":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"breadcrumb":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961#breadcrumb"},"inLanguage":"en-GB","potentialAction":[{"@type":"ReadAction","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961"]}]},{"@type":"ImageObject","inLanguage":"en-GB","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961#primaryimage","url":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4.jpg","contentUrl":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4.jpg"},{"@type":"BreadcrumbList","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=961#breadcrumb","itemListElement":[{"@type":"ListItem","position":1,"name":"Home","item":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog"},{"@type":"ListItem","position":2,"name":"Pentavalent nitrogen and boron"}]},{"@type":"WebSite","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#website","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/","name":"Henry Rzepa&#039;s Blog","description":"Chemistry with a twist","potentialAction":[{"@type":"SearchAction","target":{"@type":"EntryPoint","urlTemplate":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?s={search_term_string}"},"query-input":{"@type":"PropertyValueSpecification","valueRequired":true,"valueName":"search_term_string"}}],"inLanguage":"en-GB"},{"@type":"Person","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281","name":"Henry Rzepa","image":{"@type":"ImageObject","inLanguage":"en-GB","@id":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g370be3a7397865e4fd161aefeb0a5a85","url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","contentUrl":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","caption":"Henry Rzepa"},"description":"Henry Rzepa is Emeritus Professor of Computational Chemistry at Imperial College London.","sameAs":["https:\/\/orcid.org\/0000-0002-8635-8390"],"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?author=1"}]}},"jetpack_publicize_connections":[],"jetpack_featured_media_url":"","jetpack_sharing_enabled":true,"jetpack_shortlink":"https:\/\/wp.me\/pDef7-fv","jetpack-related-posts":[{"id":984,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=984","url_meta":{"origin":961,"position":0},"title":"Uncompressed Monovalent Helium","author":"Henry Rzepa","date":"October 3, 2009","format":false,"excerpt":"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.\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":"Inventing the  Helium bond","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/10\/C4-He.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":17829,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17829","url_meta":{"origin":961,"position":1},"title":"First, hexacoordinate carbon &#8211; now pentacoordinate nitrogen?","author":"Henry Rzepa","date":"March 25, 2017","format":false,"excerpt":"A few years back I followed a train of thought here which ended with hexacoordinate carbon, then a hypothesis rather than a demonstrated reality. That reality was recently confirmed via a crystal structure,\u00a0DOI:10.5517\/CCDC.CSD.CC1M71QM. Here is a\u00a0similar proposal for\u00a0penta-coordinate nitrogen. First, a search of the CSD (Cambridge structure database) for such\u00a0nitrogen.\u2026","rel":"","context":"In &quot;Bond slam&quot;","block_context":{"text":"Bond slam","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2237"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":4479,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=4479","url_meta":{"origin":961,"position":2},"title":"Hexavalent carbon revisited (and undecavalent boron thrown in).","author":"Henry Rzepa","date":"June 26, 2011","format":false,"excerpt":"A little while ago, I speculated (blogs are good for that sort of thing) about hexavalent carbon, and noted how one often needs to make (retrospectively) obvious connections between two different areas of chemistry. That post has attracted a number of comments in the two years its been up, along\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.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/06\/CB11.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":1278,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=1278","url_meta":{"origin":961,"position":3},"title":"The nature of the C\u2261S triple bond: part 3.","author":"Henry Rzepa","date":"December 6, 2009","format":false,"excerpt":"In the previous two posts, a strategy for tuning the nature of the CS bond in the molecule HO-S\u2261C-H was developed, based largely on the lone pair of electrons identified on the carbon atom. By replacing the HO group by one with greater \u03c3-electron withdrawing propensity, the stereo-electronic effect between\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 H2BSCH molecule. Click for 3D.","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/12\/CSBH2.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":17633,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17633","url_meta":{"origin":961,"position":4},"title":"George Olah and the norbornyl cation.","author":"Henry Rzepa","date":"March 10, 2017","format":false,"excerpt":"George Olah passed away on March 8th. He was part of the generation of scientists in the post-war 1950s who had access to chemical instrumentation that truly revolutionised chemistry. In particular he showed how the then newly available NMR spectroscopy illuminated structures of cations in solvents such \"Magic acid\". 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":936,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=936","url_meta":{"origin":961,"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","author_category":"1","first_name":"Henry","last_name":"Rzepa","user_url":"https:\/\/orcid.org\/0000-0002-8635-8390","job_title":"","description":"Henry Rzepa is Emeritus Professor of Computational Chemistry at Imperial College London."}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/961","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=961"}],"version-history":[{"count":0,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/961\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=961"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=961"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=961"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=961"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}