{"id":6069,"date":"2012-01-21T10:44:38","date_gmt":"2012-01-21T10:44:38","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=6069"},"modified":"2012-01-21T11:09:08","modified_gmt":"2012-01-21T11:09:08","slug":"the-xe-au-bond","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=6069","title":{"rendered":"The &#8220;shocking&#8221; Xe-Au bond."},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"6069\">\n<p>Chemistry rarely makes it to the cover of popular science magazines. Thus when this week, the New Scientist ran the headline &#8220;<em>Forbidden chemistry. Reactions they said could never happen<\/em>&#8220;, I was naturally intrigued. The examples included Woodward and Hoffmann&#8217;s &#8220;<em>symmetry-forbidden<\/em>&#8221; reactions, which have been the subject of several posts here already. But in the section on nobel gas chemistry, the same Hoffmann is reported as having been shocked to hear of a compound of xenon and gold, both of which in their time were thought of as solidly inert, and therefore even more unlikely to form a union.<\/p>\n<p><img decoding=\"async\" class=\"aligncenter size-full wp-image-6070\" title=\"auxe\" onclick=\"jmolInitialize('..\/Jmol\/');jmolSetAppletColor('green');jmolApplet([450,450],'load wp-content\/uploads\/2012\/01\/icsd_411365.mol;measure 1 2;');\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/01\/auxe.svg\" alt=\"\" \/><br \/>\nScience magazines are often fearful of showing molecular structures on their pages (much like mathematical equations) and so the &#8220;shocking&#8221; compound is not illustrated in the article; you can see the essential feature above (the counterion is the otherwise unremarkable Sb<sub>2<\/sub>F<sub>11<\/sub><sup>&#8211;<\/sup>). Here, I include the 3D crystallographic coordinates (published in <a href=\"http:\/\/dx.doi.org\/10.1126\/science.290.5489.117\" target=\"_blank\">10.1126\/science.290.5489.117<\/a>)\u00a0which you can explore by clicking on the above graphic or view below as a rotatable 3D model.<\/p>\n<p>Since the year 2000, when the above was reported, there have been very few additional examples, and so it remains a rare phenomenon. I thought it might be amusing to also give an example of the reverse phenomenon, a reaction that chemists said <em>should<\/em> happen, but which they had great difficulty in inducing, namely the formation of <strong><em>perbromate<\/em><\/strong> salts. The reaction was <a href=\"http:\/\/dx.doi.org\/10.1021\/ja01009a040\" target=\"_blank\">eventually induced<\/a> by resorting to nuclear physics, and the radioactive transmutation of Se<sup>83<\/sup> to Br<sup>83<\/sup>. Once chemists had been persuaded it really could be made, lots of more conventional ways of preparing perbromates were discovered.<\/p>\n<p>Finally, I ponder how long it might take for magazines such as New Scientist to include interactive diagrams such as the below on the pages of the (increasingly) electronically delivered editions? Or indeed, when mainstream chemistry journals might start incorporating &#8220;HTML5&#8221; into their own production processes.<\/p>\n<p><script type=\"text\/javascript\">\/\/ < ![CDATA[\n\/\/ < ![CDATA[\n\/\/ < ![CDATA[\n\/\/ < ![CDATA[\n\/\/ < ![CDATA[\n    var transformBallAndStick2 = new ChemDoodle.TransformCanvas3D('transformBallAndStick2', 450, 450);         transformBallAndStick2.specs.set3DRepresentation('Ball and Stick');         transformBallAndStick2.specs.backgroundColor = 'white';         var molFile = httpGet( 'wp-content\/uploads\/2012\/01\/icsd_411365.mol' );         var molecule = ChemDoodle.readMOL(molFile, 2);         transformBallAndStick2.loadMolecule(molecule);\n\/\/ ]]><\/script><\/p>\n<p>&nbsp;<\/p>\n<!-- kcite active, but no citations found -->\n<\/div> <!-- kcite-section 6069 -->","protected":false},"excerpt":{"rendered":"<p>Chemistry rarely makes it to the cover of popular science magazines. Thus when this week, the New Scientist ran the headline &#8220;Forbidden chemistry. Reactions they said could never happen&#8220;, I was naturally intrigued. The examples included Woodward and Hoffmann&#8217;s &#8220;symmetry-forbidden&#8221; reactions, which have been the subject of several posts here already. But in the section [&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":[7,4],"tags":[795,797,437,796],"ppma_author":[2661],"class_list":["post-6069","post","type-post","status-publish","format-standard","hentry","category-hypervalency","category-interesting-chemistry","tag-new-scientist","tag-nobel-gas-chemistry","tag-scientist","tag-the-new-scientist"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.5 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>The &quot;shocking&quot; Xe-Au bond. - 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=6069\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"The &quot;shocking&quot; Xe-Au bond. - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"Chemistry rarely makes it to the cover of popular science magazines. Thus when this week, the New Scientist ran the headline &#8220;Forbidden chemistry. Reactions they said could never happen&#8220;, I was naturally intrigued. The examples included Woodward and Hoffmann&#8217;s &#8220;symmetry-forbidden&#8221; reactions, which have been the subject of several posts here already. 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He spent the rest of his long life railing against the state of\u2026","rel":"","context":"In &quot;Historical&quot;","block_context":{"text":"Historical","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=565"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/11\/affinity%2Bresultant.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":4814,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=4814","url_meta":{"origin":6069,"position":1},"title":"Mindless chemistry or creative science?","author":"Henry Rzepa","date":"September 3, 2011","format":false,"excerpt":"The (hopefully tongue-in-cheek) title Mindless chemistry was given to an article reporting an automated stochastic search procedure for locating all possible minima with a given composition using high-level quantum mechanical calculations. \"Many new structures, often with nonintuitive geometries, were found\". Well, another approach is to follow unexpected hunches. One such\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\/09\/fe2.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":14224,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=14224","url_meta":{"origin":6069,"position":2},"title":"The 2015 Bradley-Mason prize for open chemistry.","author":"Henry Rzepa","date":"June 26, 2015","format":false,"excerpt":"Open principles in the sciences in general and chemistry in particular are increasingly nowadays preached from funding councils down, but it can be more of a challenge to find innovative\u00a0practitioners. Part of the problem perhaps is that many of the current reward systems for scientists do not always help promote\u2026","rel":"","context":"In &quot;Bradley-Mason Prize for Open Chemistry&quot;","block_context":{"text":"Bradley-Mason Prize for Open Chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2131"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":21051,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=21051","url_meta":{"origin":6069,"position":3},"title":"Anniversaries: The World-Wide-Web at 30 and  25 (+ CERN&#8217;s LHC as a bonus).","author":"Henry Rzepa","date":"June 15, 2019","format":false,"excerpt":"\u00a0 The World-Wide-Web is currently celebrating its 30th anniversary; you can get the T-shirt in the CERN visitor centre! \u00a0Five years on, in May 1994, the first Web conference took place (WWW94) at CERN and now celebrating its own 25th anniversary. That 1994 conference also had various break-out sessions, one\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\/2019\/06\/IMG_5076-150x150.jpg?resize=350%2C200&ssl=1","width":350,"height":200,"srcset":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2019\/06\/IMG_5076-150x150.jpg?resize=350%2C200&ssl=1 1x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2019\/06\/IMG_5076-150x150.jpg?resize=525%2C300&ssl=1 1.5x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2019\/06\/IMG_5076-150x150.jpg?resize=700%2C400&ssl=1 2x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2019\/06\/IMG_5076-150x150.jpg?resize=1050%2C600&ssl=1 3x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2019\/06\/IMG_5076-150x150.jpg?resize=1400%2C800&ssl=1 4x"},"classes":[]},{"id":45,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=45","url_meta":{"origin":6069,"position":4},"title":"Pericyclic assistance for SN-1 solvolysis","author":"Henry Rzepa","date":"April 3, 2009","format":false,"excerpt":"\u00a0 The reaction above is ostensibly a very simple pericyclic ring opening of a cyclopropyl carbocation to an allyl cation, preceeded by a preparatory step involving SN-1 solvolysis. As a 2-electron thermal process, the second step proceeds with disrotation of the terminii. Can this stereochemistry be illustrated with a computed\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":"Pericylically assisted solvolysis. Click above to see model.","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/04\/p23.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":745,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=745","url_meta":{"origin":6069,"position":5},"title":"Spotting the unexpected: Anomeric effects","author":"Henry Rzepa","date":"September 18, 2009","format":false,"excerpt":"Chemistry can be very focussed nowadays. This especially applies to target-driven synthesis, where the objective is to make a specified molecule, in perhaps as an original manner as possible. A welcome, but not always essential aspect of such syntheses is the discovery of new chemistry. In this blog, I will\u2026","rel":"","context":"In &quot;Chemical IT&quot;","block_context":{"text":"Chemical IT","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2"},"img":{"alt_text":"A cyano-substituted cis decalin","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/09\/anomeric-cn.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\/6069","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=6069"}],"version-history":[{"count":30,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/6069\/revisions"}],"predecessor-version":[{"id":6080,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/6069\/revisions\/6080"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=6069"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=6069"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=6069"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=6069"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}