{"id":4893,"date":"2011-09-18T10:09:01","date_gmt":"2011-09-18T10:09:01","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=4893"},"modified":"2011-09-20T09:49:01","modified_gmt":"2011-09-20T09:49:01","slug":"some-fun-with-no-go-areas-of-chemistry-cyclobutadiene","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=4893","title":{"rendered":"Some fun with no-go areas of chemistry: cyclobutadiene."},"content":{"rendered":"
\n

Organic chemistry has some no-go areas, where few molecules dare venture. One of them is described by a concept known as anti-aromaticity. Whereas aromatic molecules are favoured species, their anti-equivalent is avoided. I previously illustrated this (H\u00fcckel rule) with cyclopropenium anion<\/a>. Now I take a look at cyclobutadiene, for which the \u03c0-system is said to be iso-electronic (where two electrons in a double bond have replaced the carbanion lone pair).<\/p>\n

\"\"<\/a>

Geometric distortions available to square cyclobutadiene<\/p><\/div>\n

The scheme above starts with a square geometry for the cyclobutadiene. This is strongly anti-aromatic, and the molecule will strive to reduce this by indulging in a geometrical distortion. The conventional distortive mechanism is into an R<\/strong> or rectangular geometry, where two of the C-C bonds get shorter and two longer. The trouble with this mode is that is does not actually prevent the \u03c0-\u03c0 overlaps which made it anti-aromatic in the first place, it just reduces the effect. Thus rectangular cyclobutadiene is still a very very reactive and unstable molecule. So here I suggest another distortion mode, shown above as the ZW<\/strong>, or zwitterionic form. This converts the species into a combination of an allylic carbocation and a secondary carbanion. The latter would be expected to pyramidalize, thus reducing those pesky \u03c0-\u03c0 overlaps.\u00a0I am unaware of such a ZW-mode ever having been previously explored.<\/p>\n

Any student of organic chemistry will be very familiar with how to go about stabilising either a carbocation or a carbanion. We need to do this, since another guiding tenet of organic chemistry is to try to avoid charge separation whenever possible (another almost no-go area). I am going to pull a surprise by evaluating the following model for this post.<\/p>\n

\"\"<\/a>

Stabilization model for cyclobutadiene<\/p><\/div>\n

    \n
  1. Firstly, two methyl groups have been placed at the carbocationic centres to stabilise the positive charge. Tertiary carbocations are of course well known to be more stable than secondary ones (I should state that methoxy groups in the same position would stabilise even more, but that is for another post).<\/li>\n
  2. The carbanion could itself be stabilised with an electron withdrawing substituent (say CN) but here I am going to stabilise it with hydrogen bonding to a guanidinium cation. This has just the right shape to form two unusual hydrogen bonds from the N-H to either of the carbanionic lone pairs we might wish to promote (dashed lines above).<\/li>\n
  3. Finally, we are going to simulate this in water as a solvent, in order to stabilize the zwitterion. One zwitterion that DOES form is of course that from the amino acid glycine, but it only forms when placed in water (and life as we know it would not be possible if amino acids did not do this).<\/li>\n<\/ol>\n
    The results are thus. The R<\/strong> distorted form does come out the most stable<\/a>\u00a0(\u03c9B97XD\/6-311G(d,p)\/SCRF=water).\u00a0An unsymmetrical ZW form<\/a>\u00a0(forming just one C…H-N hydrogen bond) is 11.2 kcal\/mol higher in free energy, whilst a symmetrical form<\/a> (as shown above, forming two C…H-N hydrogen bonds) is only 8.5 kcal\/mol higher in free energy. It turns out that the R<\/strong> form of the 1,3-dimethylcyclobutadiene is itself stabilised by hydrogen bonding to the guanidinium cation. These hydrogen bonds form to the centre of the shortened C=C alkene bonds rather than being directed at an atom (\u03c0-facial bonding). In contrast, the ZW<\/strong> forms sustain hydrogen bonds directly to the carbons. To explore these unusual features, click on any of the three thumbnails below.<\/div>\n\n\n\n\n
    R form<\/td>\nZW-u form<\/td>\nZW-s form<\/td>\n<\/tr>\n
    \"\"

    CBD R form. Click for 3D<\/p><\/div><\/td>\n

    \"\"

    Zwitterionic form. Click for 3D.<\/p><\/div><\/td>\n

    \"\"

    Zwitterionic symmetric form. Click for 3D<\/p><\/div><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

    Where have the electrons gone in e.g.<\/em> the symmetric ZW system?\u00a0An ELF analysis tells us. The two ELF basins labelled with green arrows contain 1.2 electrons each. The basins corresponding to the 4-ring are labelled with magenta arrows. Put simply, 2.4 electrons have fled the ring, and associated themselves instead with the N-H…C hydrogen bonds. By removing ~2 electrons from an anti-aromatic ring, one converts it into an aromatic one (4n => 4n+2)!<\/p>\n

    \"\"

    ELF analysis. Click for 3D<\/p><\/div>We have learned that the highly reactive alkene bonds in R<\/strong>-distorted cyclobutadiene can be reasonable hydrogen bond donors, but that an alternative distortion into a zwitterionic form can be stabilised by forming an even stronger hydrogen bond to the forming carbanion. A symmetric form of this latter is unusual, since it still sustains four equal C-C bond lengths, but anti-aromaticity is now avoided by pyramidalising two of the carbons and hydrogen bonding to them both. As I noted earlier, these isomers of cyclobutadiene have not hitherto been proposed, and they do seem good candidates for experimental investigations.<\/p>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    Organic chemistry has some no-go areas, where few molecules dare venture. One of them is described by a concept known as anti-aromaticity. Whereas aromatic molecules are favoured species, their anti-equivalent is avoided. I previously illustrated this (H\u00fcckel rule) with cyclopropenium anion. Now I take a look at cyclobutadiene, for which the \u03c0-system is said to […]<\/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":[272,662,40,661,373,667],"ppma_author":[2661],"class_list":["post-4893","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-cyclobutadiene","tag-following-model-for-this-post","tag-free-energy","tag-glycine","tag-tutorial-material","tag-zwitterion"],"yoast_head":"\nSome fun with no-go areas of chemistry: cyclobutadiene. - 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=4893\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Some fun with no-go areas of chemistry: cyclobutadiene. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"Organic chemistry has some no-go areas, where few molecules dare venture. One of them is described by a concept known as anti-aromaticity. Whereas aromatic molecules are favoured species, their anti-equivalent is avoided. I previously illustrated this (H\u00fcckel rule) with cyclopropenium anion. 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The simplest such system would be the triplet state of cyclobutadiene, for which a non or anti-aromatic singlet state is always found to\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\/2019\/01\/CBD-1024x717.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":10498,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498","url_meta":{"origin":4893,"position":1},"title":"Au and Pt \u03c0-complexes of cyclobutadiene.","author":"Henry Rzepa","date":"May 15, 2013","format":false,"excerpt":"In the preceding post, I introduced Dewar's\u00a0\u03c0-complex theory for alkene-metal compounds, outlining the molecular orbital analysis he presented, in which the filled \u03c0-MO of the alkene donates into a Ag+\u00a0empty metal orbital and back-donation occurs from a filled metal orbital into the alkene \u03c0* MO. Here I play a little\u2026","rel":"","context":"In "Hypervalency"","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"Pt-cbd","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/Pt-cbd.jpeg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":17543,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17543","url_meta":{"origin":4893,"position":2},"title":"Stable “unstable” molecules: a crystallographic survey of cyclobutadienes and cyclo-octatetraenes.","author":"Henry Rzepa","date":"March 5, 2017","format":false,"excerpt":"Cyclobutadiene is one of those small iconic molecules, the transience and instability of which was explained theoretically long before it was actually detected in 1965. Given that instability, I was intrigued as to how many crystal structures might have been reported for this ring system, along with the rather more\u2026","rel":"","context":"In "crystal_structure_mining"","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/134-1024x722.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":2828,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=2828","url_meta":{"origin":4893,"position":3},"title":"Can a cyclobutadiene and carbon dioxide co-exist in a calixarene cavity?","author":"Henry Rzepa","date":"November 19, 2010","format":false,"excerpt":"On 8th August this year, I posted on a fascinating article that had just appeared in Science in which the crystal structure was reported of two small molecules,\u00a01,3-dimethyl cyclobutadiene\u00a0and\u00a0carbon dioxide, entrapped together inside a calixarene cavity. Other journals (e.g.\u00a0Nature Chemistry ran the article as a research highlight (where the purpose\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\/11\/cbd.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":9894,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9894","url_meta":{"origin":4893,"position":4},"title":"To be cyclobutadiene, or not to be, that is the question? You decide.","author":"Henry Rzepa","date":"March 21, 2013","format":false,"excerpt":"A quartet of articles has recently appeared on the topic of cyclobutadiene.,,,. You will find a great deal discussed there, but I can boil it down to this essence. Do the following coordinates (obtained from a (disordered) previously published x-ray refinement) correspond to a van der Waals complex of 1,3-dimethyl\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":"","width":0,"height":0},"classes":[]},{"id":7027,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=7027","url_meta":{"origin":4893,"position":5},"title":"Joining up the pieces. Peroxidation of ethyne.","author":"Henry Rzepa","date":"July 9, 2012","format":false,"excerpt":"Sometimes, connections between different areas of chemistry just pop out (without the help of semantic web tools, this is called serendipity). So here, I will try to join up some threads which emerge from previous posts. I had noted that antiaromaticity in cyclopropenium anion is lessened by the system adopting\u2026","rel":"","context":"In "Curly arrows"","block_context":{"text":"Curly arrows","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2327"},"img":{"alt_text":"","src":"","width":0,"height":0},"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\/4893","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=4893"}],"version-history":[{"count":0,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/4893\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=4893"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=4893"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=4893"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=4893"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}