{"id":23062,"date":"2020-12-04T05:35:39","date_gmt":"2020-12-04T05:35:39","guid":{"rendered":"https:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=23062"},"modified":"2020-12-04T05:35:39","modified_gmt":"2020-12-04T05:35:39","slug":"is-cyanogen-chloride-fluoride-a-source-of-c%e2%a9%b8n-more-mechanistic-insights","status":"publish","type":"post","link":"https:\/\/www.rzepa.net\/blog\/?p=23062","title":{"rendered":"Is cyanogen chloride (fluoride) a source of C\u2a78N(+)? More mechanistic insights."},"content":{"rendered":"
\n

I asked the question in my previous post<\/a>. A computational mechanism revealed that AlCl3<\/sub> or its dimer Al2<\/sub>Cl6<\/sub> could catalyse a concerted 1,1-substitution reaction at the carbon of Cl-C\u2261N, with benzene displacing chloride which is in turn captured by the Al. Unfortunately the calculated barrier for this simple process was too high for a reaction apparently occuring at ~room temperatures. Comments on the post suggested using either a second AlCl3<\/sub> or a proton to activate the carbon of the C\u2261N group by coordination on to nitrogen. A second suggestion was to involve di-cationic electrophiles. Here I report the result of implementing the N-coordinated model below.<\/p>\n

\"\"

Click on image for \u00a03D model<\/p><\/div>\n

The free energy barrier \u0394G\u2021<\/sup>298<\/sub> is 20.8 kcal\/mol (FAIR Data DOI: 10.14469\/hpc\/7584<\/a>), which corresponds to a facile reaction at room temperatures. There does not seem to be any need to invoke super-reactive di-cationic electrophiles in this instance.\u00a0This is yet another illustration that computational modelling nowadays is good enough to flag unviable mechanisms, and hence to instigate a search for a better model.<\/p>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

I asked the question in my previous post. A computational mechanism revealed that AlCl3 or its dimer Al2Cl6 could catalyse a concerted 1,1-substitution reaction at the carbon of Cl-C\u2261N, with benzene displacing chloride which is in turn captured by the Al. Unfortunately the calculated barrier for this simple process was too high for a reaction […]<\/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,"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":[1085],"tags":[],"class_list":["post-23062","post","type-post","status-publish","format-standard","hentry","category-reaction-mechanism-2"],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"","jetpack_sharing_enabled":true,"jetpack_shortlink":"https:\/\/wp.me\/p1gPyz-5ZY","jetpack_likes_enabled":true,"_links":{"self":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts\/23062","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=23062"}],"version-history":[{"count":0,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts\/23062\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=23062"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=23062"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=23062"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}