{"id":10937,"date":"2013-07-27T15:28:15","date_gmt":"2013-07-27T14:28:15","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=10937"},"modified":"2023-09-16T18:28:14","modified_gmt":"2023-09-16T17:28:14","slug":"vsepr-theory-a-closer-look-at-chlorine-trifluoride-clf3","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10937","title":{"rendered":"VSEPR Theory: A closer look at chlorine trifluoride, ClF3."},"content":{"rendered":"
\n

Valence shell electron pair repulsion theory is a simple way of rationalising the shapes of many compounds in which a main group element is surrounded by ligands. ClF3<\/sub> is a good illustration of this theory.<\/p>\n

\"ClF3\"<\/p>\n

The standard application<\/a> of VSEPR theory to this molecule is as follows:<\/p>\n

    \n
  1. Central atom: chlorine<\/span><\/li>\n
  2. Valence electrons on central atom: 7<\/li>\n
  3. Three fluorine atoms contribute: 1 each<\/li>\n
  4. Total: 10<\/strong> = five electron pairs<\/strong>.<\/li>\n
  5. The highest repulsion is between any two “lone electron pairs”, resulting in these moving apart as far as possible<\/li>\n
  6. the next highest is between one lone pair and a bond pair<\/li>\n
  7. the lowest is between two bond pairs.<\/li>\n<\/ol>\n

    \u00a0As applied to chlorine trifluoride<\/a>, it results in a trigonal bipyramidal<\/strong> geometry for the shape-determining five electron pairs. One of the trigonal positions is occupied by the pair deriving from a Cl-F bond (F=white, Cl=red below). The other two trigonal positions are occupied by two sets of electron lone pairs (yellow below) at \u2265 120\u00b0 (rule 5, but much more and the repulsions between the lone pair and the \u00a0trigonal Cl-F bond would become too great, rule 6 above). The remaining two Cl-F bond pairs occupy the di-axial positions (rule 7 above).<\/p>\n

    \"VSEPR\"<\/p>\n

    The above at least is the standard “text-book” picture. Regular readers of this blog may have noted that I often like to question the text books. So here goes. My issue is with the above explanation, of five electron pairs all associated in some way with the central atom. An expanded octet in other words. Well, if you take a look at earlier blogs<\/a>, you may have observed that this expanded octet is not real (IMHO). If it’s not real, then we cannot be dealing with five electron pairs. Can VSEPR work with only eight electrons in this instance? And what are the coordinates of the so-called two “lone pairs”: is the angle subtended at the Cl by them really trigonal (~120)?<\/p>\n

    I start with computing an accurate wavefunction, using the DFT-based \u03c9B97XD\/6-311++G(d,p)[1]<\/a><\/span>. The electron count and the coordinates of the localised basins will be obtained using ELF (Electron localisation function).<\/p>\n

    \"Click

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

      \n
    1. The electron basins are shown here as red spheres; 8 and 9 are the “lone pairs”, as it happens a very reasonable description since the populations for these are 2.07e. The 8-2-9 angle of 154\u00b0\u00a0results from rule 5 above; lone pairs repel greatly. Indeed, one might almost describe 8 and 9 as being di-axial. In which case, the geometry is not that of a trigonal bipyramid but is closer to that of a square pyramid<\/strong>.<\/li>\n
    2. Basin 7 is a Cl-F bond, with a population of 0.87e, rather less than a “pair” (the Wiberg bond index is 0.82).<\/li>\n
    3. Basins 11+19 and 10+15 (similar basin splitting\u00a0is observed<\/a>\u00a0for F2<\/sub>[2]<\/a><\/span>)\u00a0each total 0.91e; again less than a pair (Wiberg index 0.63).\u00a0\u00a0So the three Cl-F bonds are < 2-electron bonds and so their mutual repulsion might be expected to be less than rule 7 above. Indeed, any small 2-electron-3-centre 1-4 or 1-3 contributions (Wiberg index 0.07) might cause these bonds to actually move together resulting in the \"T\" shape in which the angle 4-2-3 is actually < 180\u00b0 (174).\u00a0<\/li>\n
    4. Other features include eg<\/em> the orientation of the “lone pairs” on fluorines 3 and 4, in which e.g. 16 is oriented anti-periplanar to the 2-1 bond. This is in fact an anomeric effect! An NBO analysis reveals E(2) between Lp16<\/sub> and \u03c3*2-1<\/sub>\u00a0to be 6.3 kcal\/mol, a relatively weak but still a real anomeric interaction.<\/li>\n
    5. The total electron count for the ELF basins surrounding the central Cl is 6.84, not 10 as was implied in the simple argument set out above.<\/li>\n<\/ol>\n

      VSEP<\/b>R theory is a highly simplified way of looking at the geometric origins of this odd little molecule; an ELF analysis likewise paints only a partial picture. Indeed, it seems doubtful that any simple way of regarding this species can ever be entirely adequate. But we should be mindful that the “EP” (electron pair) of VSEPR might itself be rather misleading in perpetuating the idea that such main group elements contain expanded octets. But the geometry of chlorine trifluoride makes sense without imposing 10 valence electrons on the chlorine after all!<\/p>\n

      \n

      See slso bromine trifluoride<\/a> and crystal data for such species.<\/a><\/p>\n

      \n

      Acknowledgments<\/h4>\n

      This post has been cross-posted in PDF format at Authorea<\/a>.<\/p>\n

      References<\/h2>\n
      1. H.S. Rzepa, \"Gaussian Job Archive for ClF3\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.757728<\/a>\n\n<\/li>\n
      2. S. Shaik, D. Danovich, B. Silvi, D.L. Lauvergnat, and P.C. Hiberty, \"Charge\u2010Shift Bonding\u2014A Class of Electron\u2010Pair Bonds That Emerges from Valence Bond Theory and Is Supported by the Electron Localization Function Approach\", Chemistry \u2013 A European Journal<\/i>, vol. 11, pp. 6358-6371, 2005. https:\/\/doi.org\/10.1002\/chem.200500265<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

        Valence shell electron pair repulsion theory is a simple way of rationalising the shapes of many compounds in which a main group element is surrounded by ligands. ClF3 is a good illustration of this theory. 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So here is a follow-up on another little molecue,\u00a0F3SN. As the name implies, it is often represented with an\u00a0S\u2261N bond. Here I take a look at the conventional analysis. This 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":"","width":0,"height":0},"classes":[]},{"id":18993,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18993","url_meta":{"origin":10937,"position":1},"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":16497,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=16497","url_meta":{"origin":10937,"position":2},"title":"A wider look at chlorine trifluoride: crystal structures and data mining.","author":"Henry Rzepa","date":"June 10, 2016","format":false,"excerpt":"A while ago, I explored how the 3-coordinate halogen compound ClF3\u00a0is conventionally analyzed using\u00a0VSEPR (valence shell electron pair repulsion theory). Here I (belatedly) look at other such tri-coordinate halogen compounds using known structures gleaned from the\u00a0crystal structure database (CSD). The search query specifies\u00a07A as the central atom, defined with just\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":"","width":0,"height":0},"classes":[]},{"id":17467,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17467","url_meta":{"origin":10937,"position":3},"title":"VSEPR Theory: A closer look at bromine trifluoride, BrF3.","author":"Henry Rzepa","date":"February 14, 2017","format":false,"excerpt":"I analysed the bonding in chlorine trifluoride a few years back in terms of VSEPR theory. I noticed that several searches on this topic which led people to this post also included a query about\u00a0the differences between it and the bromine analogue. For those who posed this question, here is\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":19251,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19251","url_meta":{"origin":10937,"position":4},"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":14272,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=14272","url_meta":{"origin":10937,"position":5},"title":"Electrides (aka solvated electrons).","author":"Henry Rzepa","date":"July 8, 2015","format":false,"excerpt":"Peter Edwards has just given the 2015 Hofmann lecture here at Imperial on the topic of solvated electrons. An organic chemist knows this species as \"e-\" and it occurs in ionic compounds known as electrides; chloride = the negative anion of a chlorine atom, hence electride = the negative anion\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":[]}],"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\/10937","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=10937"}],"version-history":[{"count":34,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/10937\/revisions"}],"predecessor-version":[{"id":26472,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/10937\/revisions\/26472"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=10937"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=10937"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=10937"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=10937"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}