{"id":2926,"date":"2010-12-02T20:46:39","date_gmt":"2010-12-02T19:46:39","guid":{"rendered":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=2926"},"modified":"2010-12-03T12:41:39","modified_gmt":"2010-12-03T11:41:39","slug":"morphing-an-arrow-pushing-tutorial-into-a-dihydrogen-bond","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=2926","title":{"rendered":"Morphing an arrow-pushing tutorial into a dihydrogen bond"},"content":{"rendered":"
\n

My university tutorial yesterday covered selective reductions of functional groups in organic chemistry. My thoughts on that topic have now morphed into something rather different. Scientific research has a habit of having this sort of thing happen.<\/p>\n

After I completed the blog post<\/a> (deliberately done whilst the memory of the tutorial was fresh on my mind), a thought then struck me. I appended a new idea to the post in the form of a comment (the actual posts themselves I feel should remain resolutely unmorphed; I tend to correct only typographical and minor errors). I had spotted that the adduct between ethanoic acid and borane had a very short H…H distance. So the obvious thing to do is to see if one might tweak the structure to further enhance the interaction. Hence below.<\/p>\n

\"\"

Acyloxy-beryllium hydride. Click for 3D<\/p><\/div>The interaction of interest is between an acidic hydrogen and the hydridic one. The former can be acidified further by employing trifluoroethanoic acid. The latter can be tweaked by replacing boron with beryllium. This newly designed molecule now exhibits a H…H distance of 1.278\u00c5 (\u03c9B97XD\/6-311G(d,p) calculation<\/a>), which as these so-called dihydrogen bonds go is pretty short (H2<\/sub> itself is ~0.74\u00c5). Normal dihydrogen bonds (see for example my lecture course<\/a>) are in the region of 2.0-2.2\u00c5, although \u00a0a few crystal structures (e.g.\u00a0WAGBAH in the Cambridge database)\u00a0have \u00a0shorter B-H…H-O distances of around \u00a01.76\u00c5. A typical \u00a0H…H van der Waals distance is \u00a0~2.4\u00c5. \u00a0So it appears that H…H interactions can be almost continuously tuned across the whole range of short covalent, to short and medium \u00a0dihydrogen and long dispersion lengths. The AIM analysis (below), shows \u03c1(r) to be ~0.07 au for the bond-critical-point spanning the H…H region. Normal hydrogen bonds rarely exceed 0.04, although it’s still some way off a covalent H-H bond value (0.26).<\/p>\n

\"\"<\/a>

AIM analysis.<\/p><\/div>\n

Could the molecule above be made and characterised? Well, it is probably the case that as the H…H distance gets shorter, so the activation barrier for actually eliminating covalent H2<\/sub> will get smaller and smaller. Probably, distances of \u00a0~1.7\u00c5 represent the shortest that actually has a reasonable barrier preventing such eliminations. With the current interest in devising materials capable of storing \u00a0H2 <\/sub>(and absorbing\/releasing it on demand), these types of molecule may perhaps prove useful. Quite a way to come starting from a tutorial on diborane reductions.<\/p>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

My university tutorial yesterday covered selective reductions of functional groups in organic chemistry. My thoughts on that topic have now morphed into something rather different. Scientific research has a habit of having this sort of thing happen. After I completed the blog post (deliberately done whilst the memory of the tutorial was fresh on my […]<\/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":[144,334,2648],"ppma_author":[2661],"class_list":["post-2926","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-cambridge","tag-dihydrogen-bond","tag-interesting-chemistry"],"yoast_head":"\nMorphing an arrow-pushing tutorial into a dihydrogen bond - 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=2926\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Morphing an arrow-pushing tutorial into a dihydrogen bond - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"My university tutorial yesterday covered selective reductions of functional groups in organic chemistry. 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The Tiffeneau-Demjanov rearrangement as part of a prostaglandin synthesis.","author":"Henry Rzepa","date":"November 23, 2015","format":false,"excerpt":"This reaction emerged a few years ago (thanks Alan!) as a tutorial problem in organic chemistry, in which students had to devise a mechanism for the reaction and use this to predict the stereochemical outcome at the two chiral centres indicated with *. \u00a0It originates in a brief report from\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":"Click for 3D","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2015\/11\/green.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\/2926","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=2926"}],"version-history":[{"count":0,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/2926\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=2926"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=2926"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=2926"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=2926"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}