{"id":19347,"date":"2018-01-13T09:37:12","date_gmt":"2018-01-13T09:37:12","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=19347"},"modified":"2018-02-25T08:44:23","modified_gmt":"2018-02-25T08:44:23","slug":"hypervalent-hydrogen","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19347","title":{"rendered":"Hypervalent hydrogen?"},"content":{"rendered":"
\n

I discussed<\/a> the molecule the molecule CH3<\/sub>F2-<\/sup> a while back. It was a very rare computed example of a system where the added two electrons populate the higher valence shells known as Rydberg orbitals as an alternative to populating the C-F antibonding \u03c3-orbital to produce CH3<\/sub>–<\/sup> and F–<\/sup>. The net result was the creation of a weak C-F “hyperbond”, in which the C-F region has an inner conventional bond, with an outer “sheath” encircling the first bond. But this system very easily dissociates to CH3<\/sub>–<\/sup> and F–<\/sup> and is hardly a viable candidate for experimental detection.\u00a0 In an effort to “tune” this effect to see if a better candidate for such detection might be found, I tried\u00a0CMe3<\/sub>F2-<\/sup>. Here is its story.<\/p>\n

The calculation\u2021<\/sup> is at the\u00a0\u03c9B97XD\/Def2-TZVPPD\/SCRF=water level (water is here used as an approximate model for a condensed environment, helping to bind the two added electrons).<\/p>\n

    \n
  1. An NBO (Natural Bond orbital) analysis reveals a total Rydberg orbital population of 1.186e and the following bond indices; F 0.853, C 3.977, C(methyl) 4.051<\/strong><\/span>, H(*3) 1.332<\/strong><\/span>.\u00a0The latter corresponds to the three methyl hydrogens aligned antiperiplanar to the C-F bond.<\/li>\n
  2. To put this value into context, the hydrogen in the FHF–<\/sup> anion has an NBO H bond index of 0.724, and the bridging hydrogens in diborane only have a value of 0.988. Even the hexa-coordinate hydride system [Co6<\/sub>H(CO)15<\/sub>]\u2013<\/sup>\u00a0discussed in an earlier blog<\/a>\u00a0 has an H bond index of just 0.86. Actually, coordination of six or even higher for hydrogen is no longer rare; some\u00a028 crystal structures of the type HM6<\/sub> (M=metal) are known (it would be useful to find out if any of the other 27 such structures might have a hydrogen bond index >1).<\/li>\n
  3. Next, the ELF analysis (Electron localisation function), analysed firstly using the excellent MultiWFN program.[1]<\/a><\/span>
    \n \"\"
    \n This reveals an attractor basin integrating to 1.663e and located along the axis of the F-C bond and extended into the region of the three antiperiplanar methyl hydrogens. The C-F bond itself only supports a basin of 0.729e, typical of the fairly ionic C-F bond. The covalent C-Me bonds are also pretty normal, as are the other hydrogens.<\/li>\n
  4. I also show ELF analysis using the alternative TopMod program[2]<\/a><\/span>; the numerical values on this diagram are the calculated bond lengths in \u00c5. The basin integrations are very similar to those obtained using MultiWFN.
    \n \"\"
    \n The Wiberg bond orders of the three H…H regions shown connected by dashed lines above are 0.154, which contributes to the bond index of >1\u00a0at these three hydrogens.<\/li>\n
  5. The predicted 1<\/sup>H chemical shift of these three “hypervalent” hydrogens is +3.0 ppm, whilst the other six methyl hydrogens are at -0.87ppm.<\/li>\n<\/ol>\n

    So changing\u00a0CH3<\/sub>F2-<\/sup> to\u00a0CMe3<\/sub>F2-<\/sup> has dramatically changed the bonding picture that emerges, rather than a fine-tuning. The C-F is no longer a “hyperbond”, although the Rydberg occupancy of 1.186e remains unusually large. Most of the additional electrons have fled the torus surrounding the C-F bond and relocated to the\u00a0exo<\/em>-region of that bond where they now influence the three antiperiplanar methyl hydrogens. A\u00a0two-electron-three-centre interaction if you like, but with the electron basin occupying a tetrahedral vertex rather than the triatom centroid.<\/p>\n

    I end with a challenge. Is it possible to find “real” molecules containing hydrogen where the formal bond index for at least one hydrogen exceeds 1.0 significantly, thus making it hypervalent?\u00a0<\/p>\n

    \n

    \u2021<\/sup>The calculations are all collected at FAIR doi; 10.14469\/hpc\/3372<\/a>.<\/p>\n

    References<\/h2>\n
    1. T. Lu, and F. Chen, \"Multiwfn: A multifunctional wavefunction analyzer\", Journal of Computational Chemistry<\/i>, vol. 33, pp. 580-592, 2011. https:\/\/doi.org\/10.1002\/jcc.22885<\/a>\n\n<\/li>\n
    2. S. Noury, X. Krokidis, F. Fuster, and B. Silvi, \"Computational tools for the electron localization function topological analysis\", Computers & Chemistry<\/i>, vol. 23, pp. 597-604, 1999. https:\/\/doi.org\/10.1016\/s0097-8485(99)00039-x<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

      I discussed the molecule the molecule CH3F2- a while back. It was a very rare computed example of a system where the added two electrons populate the higher valence shells known as Rydberg orbitals as an alternative to populating the C-F antibonding \u03c3-orbital to produce CH3– and F–. The net result was the creation of […]<\/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":[7],"tags":[1675,2362,557,237,1395,157,1515,1871],"ppma_author":[2661],"class_list":["post-19347","post","type-post","status-publish","format-standard","hentry","category-hypervalency","tag-antibonding-molecular-orbital","tag-candidate-for-experimental-detection","tag-chemical-bonding","tag-chemical-shift","tag-chemistry","tag-metal","tag-molecular-orbital","tag-nature"],"yoast_head":"\nHypervalent hydrogen? - Henry Rzepa'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=19347\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Hypervalent hydrogen? - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"I discussed the molecule the molecule CH3F2- a while back. It was a very rare computed example of a system where the added two electrons populate the higher valence shells known as Rydberg orbitals as an alternative to populating the C-F antibonding \u03c3-orbital to produce CH3– and F–. The net result was the creation of […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19347\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2018-01-13T09:37:12+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2018-02-25T08:44:23+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2018\/01\/MeCF2-ELF-965x1024.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=\"3 minutes\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Hypervalent hydrogen? - Henry Rzepa'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=19347","og_locale":"en_GB","og_type":"article","og_title":"Hypervalent hydrogen? - Henry Rzepa's Blog","og_description":"I discussed the molecule the molecule CH3F2- a while back. It was a very rare computed example of a system where the added two electrons populate the higher valence shells known as Rydberg orbitals as an alternative to populating the C-F antibonding \u03c3-orbital to produce CH3– and F–. 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One example of a molecule so characterised was CLi6 where the description \"\u201ccarbon can expand its octet of electrons to form this relatively stable molecule\u201c was used.\u2026","rel":"","context":"In "Bond slam"","block_context":{"text":"Bond slam","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2237"},"img":{"alt_text":"CH4","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2016\/02\/CH4.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":19073,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19073","url_meta":{"origin":19347,"position":1},"title":"Hypervalence and octet-expansion in sulfur hexafluoride.","author":"Henry Rzepa","date":"November 20, 2017","format":false,"excerpt":"Following on from discussing octet expansion in species such as SeMe6, ClMe3 and ClMe5, I felt impelled to return to SF6, often used as an icon for hypervalence. With this molecule we have twelve electrons to partition, six from sulfur and one each from six fluorines (the other six electrons\u2026","rel":"","context":"In "Hypervalency"","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\/2017\/11\/SF6-HIOMO-17-1024x885.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":18768,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18768","url_meta":{"origin":19347,"position":2},"title":"Two new types in the chemical bonding zoo: exo-bonds and hyper-bonds?","author":"Henry Rzepa","date":"September 6, 2017","format":false,"excerpt":"The chemical bond zoo is relatively small (the bond being a somewhat fuzzy concept, I am not sure there is an actual count of occupants). So when two new candidates come along, it is worth taking notice.\u00a0I have previously noted the Chemical Bonds at the 21st Century-2017: CB2017\u00a0Aachen conference, where\u2026","rel":"","context":"In "Bond slam"","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":3462,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3462","url_meta":{"origin":19347,"position":3},"title":"Shorter is higher: the strange case of diberyllium.","author":"Henry Rzepa","date":"January 21, 2011","format":false,"excerpt":"Much of chemistry is about bonds, but sometimes it can also be about anti-bonds. It is also true that the simplest of molecules can have quite subtle properties. Thus most undergraduate courses in chemistry deal with how to describe the bonding in the diatomics of the first row of the\u2026","rel":"","context":"In "Interesting chemistry"","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\/Be2a.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":18975,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18975","url_meta":{"origin":19347,"position":4},"title":"Hypervalence revisited. The odd case of hexamethyl selenium.","author":"Henry Rzepa","date":"November 7, 2017","format":false,"excerpt":"One thread that runs through this blog is that of hypervalency. It was therefore nice to come across a recent review of the concept which revisits the topic, and where a helpful summary is given of the evolving meanings over time of the term hypervalent. The key phrase \"it soon\u2026","rel":"","context":"In "Hypervalency"","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\/2017\/11\/165-1024x1008.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":1887,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=1887","url_meta":{"origin":19347,"position":5},"title":"The conformation of 1,2-difluoroethane","author":"Henry Rzepa","date":"April 6, 2010","format":false,"excerpt":"Here I offer another spin-off from writing a lecture course on conformational analysis. This is the famous example of why 1,2-difluoroethane adopts a gauche rather than antiperiplanar conformation. One major contribution to the greater stability of the gauche is the stereoelectronic interactions, and this is best probed using the NBO\u2026","rel":"","context":"In "Interesting chemistry"","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\/2010\/04\/difluoroethane.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\/19347","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=19347"}],"version-history":[{"count":7,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/19347\/revisions"}],"predecessor-version":[{"id":19357,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/19347\/revisions\/19357"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=19347"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=19347"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=19347"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=19347"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}