{"id":19307,"date":"2017-12-26T09:35:21","date_gmt":"2017-12-26T09:35:21","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=19307"},"modified":"2018-02-25T08:45:35","modified_gmt":"2018-02-25T08:45:35","slug":"are-diazomethanes-hypervalent-molecules-an-attempt-into-more-insight-by-more-tuning-with-substituents","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19307","title":{"rendered":"Are diazomethanes hypervalent molecules? An attempt into more insight by more “tuning” with substituents."},"content":{"rendered":"
\n

Recollect the suggestion<\/a>\u00a0that diazomethane has hypervalent character[1]<\/a><\/span>. When I looked into this, I came to the conclusion that it probably was mildly hypervalent, but on carbon and not nitrogen. Here I try some variations with substituents to see what light if any this casts.
\n \"\"<\/a><\/p>\n

I have expanded the resonance forms of diazomethane by one structure from those shown in the previous two posts (a form by the way not considered in the original article[1]<\/a><\/span>) to include a nitrene. This takes us back to an earlier suggestion<\/a>\u00a0on this blog that HC\u2261S\u2261CH is not a stable species but a higher order saddle point which distorts down to a bis<\/em>-carbene, together with the suggestion that hypervalent triple bonds have the option of converting four of the six electrons into two carbene lone pairs, replacing the triple bond with a single bond. This in turn harks back to G. N. Lewis’<\/a> 101 year old idea for acetylene itself!<\/p>\n

To explore this mode, I start by replacing the terminal \u2261N in diazomethane with a \u2261C-Me group, which cannot absorb electrons into lone-pairs in the manner that nitrogen can. A \u03c9B97XD\/Def2-TZVPP calculation\u2021<\/sup> reveals that the linear form is a transition state for interconversion into a carbene. The IRC for the process (below) shows this carbene is ~10 kcal\/mol lower than the linear “hypervalent” form.\u00a0<\/p>\n

\"\"<\/a><\/p>\n

NBO analysis of this transition state reveals a similar orbital pattern to diazomethane itself, including a non-bonding orbital on the H2<\/sub>C carbon. The Wiberg carbon bond indices are 3.6764 and N 3.6454 and the bond orders C=N 1.1390 and N=CMe 1.6192.<\/p>\n

\"\"<\/p>\n

ELF analysis of this transition state reveals the presence of two non-bonding pairs on the carbon atoms either side of the nitrogen but unshared with it, with populations of 1.19e and 1.37e (DFT). That nitrogen really does not like excess electrons! The four atoms C,N,C,C have ELF valence basins totalling 8.00, 6.94, 7.69 and 7.92e (DFT) or 8.07, 7.07 and 7.61e (CASSCF), suggesting that unlike diazomethane itself, the octet-excess induced hypervalence on carbon is slightly decreased.<\/p>\n

\"\"<\/p>\n

\"\"<\/p>\n

Pumping even more electrons in by replacing the \u2261C-Me group with \u2261C-NH2<\/sub> does not increase any hypervalence, but does induce more electrons to reside in “lone pairs”. Of the four atoms along the chain, three have “lone pairs” associated with them, a total of 4.83e that do not contribute to bonds (valence).<\/p>\n

\"\"<\/p>\n

An electron withdrawing \u2261C-CN group replacing the\u00a0\u2261C-NH2<\/sub> reverses the effect of the latter, but this linear species is still a transition state for carbon isomerisation:<\/p>\n

\"\"<\/p>\n

Finally, combining all we have learnt by adding in nitro groups on the first carbon. This is no longer a transition state but now a stable species; the sum of the ELF basin integrations around the carbon on the left reaches 8.95e, slightly higher than the dinitro-diazomethane discussed in the previous post. The numerical Wiberg atom bond indices are C 3.8713, N 3.6898, C 3.8503, C 3.9958 and N\u00a03.0288 for the atoms along the chain, with the first nitrogen the “least-valent”.\"\"<\/p>\n

So we see that “hypervalence”, or at least “octet-excess”, which is not exactly the same as hypervalence since it includes contributions from non-bonding electrons, is balanced on a knife-edge. Trying to increase the octet-excess by pumping electrons in turns the system into a transition state for carbene formation. Octet-excess is seen as a metastable property, to be relieved by geometric distortions where possible or localization of electrons into non-bonding lone pairs. And I remind yet again that no evidence has manifested in calculations of the molecules above that the central nitrogen of these diazomethane-like systems has any propensity for octet or valence-excess as implied by the formula\u00a0C=N\u2261X.[1]<\/a><\/span><\/p>\n

\n

\u2021<\/sup>FAIR data for all calculations is available at DOI:\u00a010.14469\/hpc\/3476<\/a><\/p>\n

References<\/h2>\n
  1. M.C. Durrant, \"A quantitative definition of hypervalency\", Chemical Science<\/i>, vol. 6, pp. 6614-6623, 2015. https:\/\/doi.org\/10.1039\/c5sc02076j<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    Recollect the suggestion\u00a0that diazomethane has hypervalent character. When I looked into this, I came to the conclusion that it probably was mildly hypervalent, but on carbon and not nitrogen. Here I try some variations with substituents to see what light if any this casts. 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An attempt into more insight by more "tuning" with substituents. - 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=19307\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Are diazomethanes hypervalent molecules? An attempt into more insight by more "tuning" with substituents. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"Recollect the suggestion\u00a0that diazomethane has hypervalent character. When I looked into this, I came to the conclusion that it probably was mildly hypervalent, but on carbon and not nitrogen. Here I try some variations with substituents to see what light if any this casts. I have expanded the resonance forms of diazomethane by one structure […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19307\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2017-12-26T09:35:21+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2018-02-25T08:45:35+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/12\/diazomethane2.svg\" \/>\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":"Are diazomethanes hypervalent molecules? 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Here I explore the effect of substituting diazomethane\u2026","rel":"","context":"In "Hypervalency"","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":19251,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19251","url_meta":{"origin":19307,"position":1},"title":"Are diazomethanes hypervalent molecules? Probably, but in an unexpected way!","author":"Henry Rzepa","date":"December 23, 2017","format":false,"excerpt":"A recently published review on hypervalency introduced a very simple way of quantifying the effect. One of the molecules which was suggested to be hypervalent using this method was diazomethane. Here I take a closer look. The new method is called the valence electron equivalent \u03b3. It is defined as\u00a0\"the\u2026","rel":"","context":"In "Hypervalency"","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":18975,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18975","url_meta":{"origin":19307,"position":2},"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":19194,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19194","url_meta":{"origin":19307,"position":3},"title":"Identification of a simplest hypervalent hydrogen fluoride anion.","author":"Henry Rzepa","date":"December 8, 2017","format":false,"excerpt":"An article with the title shown above in part recently appeared. Given the apparent similarity of HF1- to CH3F1- and CH3F2-, the latter of which I introduced on this blog previously,\u00a0I thought it of interest to apply my analysis to HF1-. The authors conclude that \"the F atom of HF\u2212\u2026","rel":"","context":"In "Hypervalency"","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":12056,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12056","url_meta":{"origin":19307,"position":4},"title":"The mechanism of diazo coupling: more hidden mechanistic intermediates.","author":"Henry Rzepa","date":"March 8, 2014","format":false,"excerpt":"The diazo-coupling reaction dates back to the 1850s (and a close association with Imperial College via the first professor of chemistry there, August von Hofmann) and its mechanism was much studied in the heyday of physical organic chemistry. Nick Greeves, purveyor of the excellent ChemTube3D site, contacted me about the\u2026","rel":"","context":"In "reaction mechanism"","block_context":{"text":"reaction mechanism","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1086"},"img":{"alt_text":"cis-diazo","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2014\/03\/cis-diazo.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":10801,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10801","url_meta":{"origin":19307,"position":5},"title":"Is CLi6 hypervalent?","author":"Henry Rzepa","date":"July 5, 2013","format":false,"excerpt":"A comment made on the previous post on the topic of hexa-coordinate carbon cited an article entitled \"Observation of hypervalent CLi6\u00a0by Knudsen-effusion mass spectrometry\" by Kudo as a amongst the earliest of evidence that such species can exist (in the gas phase). It was a spectacular vindication of the earlier\u2026","rel":"","context":"In "Hypervalency"","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"Click for 3D","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/07\/CLi6-Lp.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\/19307","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=19307"}],"version-history":[{"count":18,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/19307\/revisions"}],"predecessor-version":[{"id":19335,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/19307\/revisions\/19335"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=19307"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=19307"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=19307"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=19307"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}