{"id":7643,"date":"2012-09-12T16:11:23","date_gmt":"2012-09-12T15:11:23","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=7643"},"modified":"2012-09-14T08:24:27","modified_gmt":"2012-09-14T07:24:27","slug":"what-is-the-range-of-values-for-a-sp3c-csp3-carbon-single-bond","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=7643","title":{"rendered":"What is the range of values for a (sp3)C-C(sp3) single bond length?"},"content":{"rendered":"
\n

Here is a challenge: what is the longest C-C bond actually determined (in which both carbon termini are sp3<\/sup> hybridised)? I pose this question since Steve Bachrach has posted<\/a> on how to stabilize long bonds by attractive dispersive interactions, and more recently\u00a0commenting<\/a> on what the longest straight chain alkane might be before dispersive interaction start to fold it (the answer appears to be C17<\/sub>).<\/p>\n

A search of the Cambridge database (the following conditions apply; structure determined at less than 160K, no errors, no disorder, and a minimum separation of 1.7\u00c5) reveals only 7 entries longer than 1.7A. The reference codes for these are FIBBOI, HOLKOI, LAGHOQ01, RIRTUH, RUNHOY, XIQRIZ, BATSIA, the latter having a value of 1.731\u00c5 (T=123K, R=4.44%, DOI: 10.1246\/cl.2012.541<\/a>). Of course, a very close inspection of the crystallography would also be needed to determine if these values are to be taken at face value.<\/p>\n

\"\"

BATSIA. Click for 3D model.<\/p><\/div>\n

If one relaxes the temperature constraint for measurement, CAZFUE01 has a claimed C-C length of 1.99\u00c5 (R=4.5%, DOI: 10.1246\/cl.2012.541<\/a>). This however represents the so-called frozen transition state for a [3,3] sigmatropic rearrangement. A\u00a0\u03c9B97XD\/6-311G(d,p)\/SCRF=dichloromethane calculation seems to indicate that this species is in fact a transition state for the [3,3] reaction, and hence that the crystal structure may in fact correspond to the mean position of the two end points of the reaction, and so be an artefact. More on this in a later post.\u00a0<\/p>\n

\"\"

CAZFUE. Click for 3D model.<\/p><\/div>\n

And I suppose one should ask what the shortest such single bond is as well as the longest. This is currently claimed to be 1.436\u00c5 for KAVKUO (10.1002\/anie.200501605<\/a>) and 1.434\u00c5 for WUDKAH (10.1016\/S0040-4020(02)00695-6<\/a>). The origins of this contraction also deserve to be more fully explored in a later post.<\/p>\n

\"\"

KAVKUO. Click for 3D<\/p><\/div>\n

 <\/p>\n

\"\"

WUDKAH. Click for 3D.<\/p><\/div>\n

Certainly, the (sp3<\/sup>)C-C(sp3<\/sup>) bond does seem to be capable of a large range of values ranging from 1.44 to at least 1.73 and possibly 1.99\u00c5.<\/p>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

Here is a challenge: what is the longest C-C bond actually determined (in which both carbon termini are sp3 hybridised)? I pose this question since Steve Bachrach has posted on how to stabilize long bonds by attractive dispersive interactions, and more recently\u00a0commenting on what the longest straight chain alkane might be before dispersive interaction start […]<\/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":[144,20],"ppma_author":[2661],"class_list":["post-7643","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-cambridge","tag-steve-bachrach"],"yoast_head":"\nWhat is the range of values for a (sp3)C-C(sp3) single bond length? - 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=7643\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"What is the range of values for a (sp3)C-C(sp3) single bond length? - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"Here is a challenge: what is the longest C-C bond actually determined (in which both carbon termini are sp3 hybridised)? I pose this question since Steve Bachrach has posted on how to stabilize long bonds by attractive dispersive interactions, and more recently\u00a0commenting on what the longest straight chain alkane might be before dispersive interaction start […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=7643\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2012-09-12T15:11:23+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2012-09-14T07:24:27+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/09\/BATSIA.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=\"2 minutes\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"What is the range of values for a (sp3)C-C(sp3) single bond length? - 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=7643","og_locale":"en_GB","og_type":"article","og_title":"What is the range of values for a (sp3)C-C(sp3) single bond length? - Henry Rzepa's Blog","og_description":"Here is a challenge: what is the longest C-C bond actually determined (in which both carbon termini are sp3 hybridised)? 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