{"id":19102,"date":"2017-11-27T14:49:54","date_gmt":"2017-11-27T14:49:54","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=19102"},"modified":"2018-02-25T08:48:58","modified_gmt":"2018-02-25T08:48:58","slug":"hypervalence-and-octet-expansion-in-trimethylene-%ce%bb6-sulfane-and-related-species","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19102","title":{"rendered":"Hypervalence and octet-expansion in trimethylene-\u03bb6-sulfane and related species."},"content":{"rendered":"
\n

Previously<\/a>: “Non-polar” species such as SeMe6<\/sub>, SMe6<\/sub>, ClMe3<\/sub>, ClMe5<\/sub> all revealed interesting properties for the Se-C, S-C or Cl-C “single” bonds. The latter two examples in particular hinted at internal structures for these single bonds, as manifested by two ELF basins for some of the bonds. Here I take a look at the related molecule where a formal double bond between carbon and the central sulfur atom replacing the single-bond might also hint at octet expansions and hypervalence.<\/p>\n

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

Starting with X=Y=Z=CH2<\/sub>,\u2021<\/sup> the calculated (\u03c9B97Xd\/Def2-TZVPP) geometry has an interesting chiral D3<\/sub>-symmetric form. The density based ELF-basin centroids are shown below, with each formal C=S \u03c0-double bond represented by two ELF basins above and below the C-S axis and with each pair of ELF basins being twisted by 48\u00b0 with respect to the other two pairs. The total valence shell count around the S is 10.98e and the octet is “expanded” (by ~3e).<\/p>\n

\"\"<\/p>\n

The orbital-based NBO approach indicates little utilisation of higher (Rydberg) atomic orbital shells (S: [core]3S(1.13)3p(3.35)3d(0.11)4p(0.02);\u00a0C: [core]2S(1.15)2p(3.77)3p(0.01)3d(0.01) ). Each S-C bond has a Wiberg bond order of\u00a01.36 (significantly less than a double bond), and the central S has an overall bond index of 4.102. There is a real mis-match between the orbital partitioning (2*1.36 = 2.72e) and the ELF partitioning (2*1.83 = 3.66e)\u00a0into the S-C bonds. The former indicates that ~two of the twelve valence electrons are entering into anti-bonding orbitals<\/strong> to reduce the total bond index from a possible six to just four, but that they still contribute to the electron-density based ELF disynaptic C-S basins. To cast light on this behaviour, successively one to three of the CH2<\/sub> groups can be replaced by O.<\/p>\n

\"\"<\/p>\n

For each “S=O” bond, we find the ELF basin population more or less halves and electrons instead populate the non-bonding O “lone pairs”. The S-C ELF populations in contrast remain approximately constant. These species therefore have “double” S=C bonds but just “single” S-O bonds. The Rydberg population increases slightly;\u00a0S: [core]3S(1.06)3p(2.95)3d(0.16)4p(0.02)) and the S bond index is 4.18 for one oxygen and\u00a0S: [core]3S(0.99)3p(2.67)3d(0.19)4p(0.02) and S bond index 4.16 for two oxygens.<\/p>\n

\"\"<\/p>\n

Sulfur trioxide (below) seems best represented by S-O rather than S=O bonds. The Rydberg population is\u00a0S: [core]3S(0.91)3p(2.41)3d(0.21)4p(0.03) and the S bond index is 4.32.<\/p>\n

\"\"<\/p>\n

Just for good measure sulfur trisulfide S(S)3<\/sub> shows rather lower lone pair population because of course it is less electronegative than oxygen, and hence has a slightly greater S-S ELF basin population. Rydberg,\u00a0S: [core]3S(1.43)3p(3.73)3d(0.21)4p(0.03) and central S bond index 4.04.<\/p>\n

\"\"<\/p>\n

It seems molecules where the electrons in a valence shell exceed the “octet” are only too happy to let the excess electrons leak out into adjacent electronegative atoms as lone pairs, where they are no longer classified as \u00a0“shared”. Trimethylene-\u03bb6-sulfane does not have this option and the excess electrons remain in the region of the valence shell, but here they do not contribute to augmenting the bond index at the central atom. \u00a0In this specific interpretation, the octet is exceeded, but hypervalence is not induced. It is a slippery concept; one where general agreement about its properties may indeed be difficult to achieve!<\/p>\n

\n

\u2021<\/sup>The FAIR data DOI collection for this post is 10.14469\/hpc\/3316<\/a>.<\/p>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

Previously: “Non-polar” species such as SeMe6, SMe6, ClMe3, ClMe5 all revealed interesting properties for the Se-C, S-C or Cl-C “single” bonds. The latter two examples in particular hinted at internal structures for these single bonds, as manifested by two ELF basins for some of the bonds. Here I take a look at the related molecule […]<\/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":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[7],"tags":[1402,557,1957,1395,1016,1679,1871,1015,2383,1634],"ppma_author":[2661],"class_list":["post-19102","post","type-post","status-publish","format-standard","hentry","category-hypervalency","tag-chemical-bond","tag-chemical-bonding","tag-chemical-polarity","tag-chemistry","tag-double-bond","tag-hypervalent-molecule","tag-nature","tag-single-bond","tag-tetravalence","tag-valence"],"yoast_head":"\nHypervalence and octet-expansion in trimethylene-\u03bb6-sulfane and related species. - 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=19102\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Hypervalence and octet-expansion in trimethylene-\u03bb6-sulfane and related species. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"Previously: “Non-polar” species such as SeMe6, SMe6, ClMe3, ClMe5 all revealed interesting properties for the Se-C, S-C or Cl-C “single” bonds. The latter two examples in particular hinted at internal structures for these single bonds, as manifested by two ELF basins for some of the bonds. 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An attempt into more insight by more “tuning” with substituents.","author":"Henry Rzepa","date":"December 26, 2017","format":false,"excerpt":"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\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\/12\/H2CNCCN_ELF-1024x258.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":19133,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19133","url_meta":{"origin":19102,"position":1},"title":"Octet expansion and hypervalence in dimethylidyne-\u03bb6-sulfane.","author":"Henry Rzepa","date":"November 28, 2017","format":false,"excerpt":"I started this story by looking at octet expansion and hypervalence in non-polar hypercoordinate species such as S(-CH3)6, then moved on to S(=CH2)3. Finally now its the turn of S(\u2261CH)2.\u2021 As the triple bonds imply, this seems to represent twelve shared valence electrons surround the sulfur, six from S itself\u2026","rel":"","context":"In "Historical"","block_context":{"text":"Historical","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=565"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/11\/HCSCH-NBO-1024x973.png?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":18993,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18993","url_meta":{"origin":19102,"position":2},"title":"VSEPR Theory: Octet-busting or not with trimethyl chlorine, ClMe3.","author":"Henry Rzepa","date":"November 12, 2017","format":false,"excerpt":"A few years back, I took a look at the valence-shell electron pair repulsion approach to the geometry of chlorine trifluoride, ClF3 using so-called ELF basins to locate centroids for both the covalent F-Cl bond electrons and the chlorine lone-pair electrons. Whereas the original VSEPR theory talks about five \"electron\u2026","rel":"","context":"In "Chemical IT"","block_context":{"text":"Chemical IT","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":19073,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19073","url_meta":{"origin":19102,"position":3},"title":"Hypervalence and octet-expansion in sulfur hexafluoride.","author":"Henry Rzepa","date":"November 20, 2017","format":false,"excerpt":"Following on from discussing octet expansion in species such as SeMe6, ClMe3 and ClMe5, I felt impelled to return to SF6, often used as an icon for hypervalence. With this molecule we have twelve electrons to partition, six from sulfur and one each from six fluorines (the other six electrons\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\/SF6-HIOMO-17-1024x885.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":18975,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18975","url_meta":{"origin":19102,"position":4},"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":1423,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=1423","url_meta":{"origin":19102,"position":5},"title":"Contriving aromaticity from S\u2261C Triple bonds","author":"Henry Rzepa","date":"January 1, 2010","format":false,"excerpt":"In the previous post, the molecule F3S-C\u2261SF3 was found to exhibit a valence bond isomerism, one of the S-C bonds being single, the other triple, and with a large barrier (~31 kcal\/mol, \u03bd 284i cm-1) to interconversion of the two valence-bond forms. So an interesting extension of this phenomenon is\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\/2010\/01\/S3C3F6.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\/19102","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=19102"}],"version-history":[{"count":19,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/19102\/revisions"}],"predecessor-version":[{"id":19127,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/19102\/revisions\/19127"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=19102"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=19102"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=19102"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=19102"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}