{"id":999,"date":"2015-02-09T15:53:25","date_gmt":"2015-02-09T23:53:25","guid":{"rendered":"http:\/\/blogs.reed.edu\/chem324\/?p=999"},"modified":"2015-02-09T15:53:25","modified_gmt":"2015-02-09T23:53:25","slug":"anions-that-can-tolerate-2-norbornyl-cation","status":"publish","type":"post","link":"https:\/\/blogs.reed.edu\/chem324\/2015\/02\/09\/anions-that-can-tolerate-2-norbornyl-cation\/","title":{"rendered":"Anions that can tolerate 2-norbornyl cation"},"content":{"rendered":"<p>I forget whether this question came up in our discussion of the <strong><a title=\"Scholz et al | Science, 2013 (DOI  10.1126\/science.1238849)\" href=\"http:\/\/www.sciencemag.org\/content\/341\/6141\/62.full\" target=\"_blank\">Scholz paper<\/a> (paper #1)<\/strong>, but 2-norbonyl cation was crystallized with Al2Br7 anion. The authors described this anion as &#8220;weakly coordinating,&#8221;<\/p>\n<blockquote><p>Our interest in binding challenging ions such as the [CX<sub>3<\/sub>]<sup>+<\/sup> (X = Cl, Br, or I) cations (<a id=\"xref-ref-35-1\" class=\"xref-bibr\" href=\"http:\/\/www.sciencemag.org\/content\/341\/6141\/62.full#ref-35\"><em>35<\/em><\/a>\u2013<a id=\"xref-ref-37-1\" class=\"xref-bibr\" href=\"http:\/\/www.sciencemag.org\/content\/341\/6141\/62.full#ref-37\"><em>37<\/em><\/a>) to weakly coordinating anions (<a id=\"xref-ref-38-1\" class=\"xref-bibr\" href=\"http:\/\/www.sciencemag.org\/content\/341\/6141\/62.full#ref-38\"><em>38<\/em><\/a>, <a id=\"xref-ref-39-1\" class=\"xref-bibr\" href=\"http:\/\/www.sciencemag.org\/content\/341\/6141\/62.full#ref-39\"><em>39<\/em><\/a>) led us to exploit the ability of soft bromoaluminate anions, such as [Al<sub>2<\/sub>Br<sub>7<\/sub>]<sup>\u2013<\/sup>, to stabilize, for example, the [C(CH<sub>3<\/sub>)<sub>3<\/sub>]<sup>+<\/sup> carbocation in the solid state (<a id=\"xref-ref-40-1\" class=\"xref-bibr\" href=\"http:\/\/www.sciencemag.org\/content\/341\/6141\/62.full#ref-40\"><em>40<\/em><\/a>).<\/p><\/blockquote>\n<p>The unusual properties of this anion leap out from a comparison of potential maps of Al2Br7 anion (left) with BF4 anion (right) (EDF2\/6-31g* made with iSpartan). Potentials on the former map never get more negative than approx. -340 kJ\/mol, while those on the latter reach much more negative values (the extreme occurs at -615 kJ\/mol in the orange-red bands between F&#8217;s).<\/p>\n<figure id=\"attachment_1000\" aria-describedby=\"caption-attachment-1000\" style=\"width: 150px\" class=\"wp-caption alignleft\"><a href=\"https:\/\/blogs.reed.edu\/chem324\/files\/2015\/02\/Al2Br7-anion.png\"><img loading=\"lazy\" decoding=\"async\" class=\"size-thumbnail wp-image-1000\" src=\"https:\/\/blogs.reed.edu\/chem324\/files\/2015\/02\/Al2Br7-anion-150x150.png\" alt=\"Al2Br7 anion\" width=\"150\" height=\"150\" \/><\/a><figcaption id=\"caption-attachment-1000\" class=\"wp-caption-text\">Al2Br7 anion (EDF2\/6-31G*, iSpartan)<\/figcaption><\/figure>\n<figure id=\"attachment_1001\" aria-describedby=\"caption-attachment-1001\" style=\"width: 150px\" class=\"wp-caption alignleft\"><a href=\"https:\/\/blogs.reed.edu\/chem324\/files\/2015\/02\/BF4-anion.png\"><img loading=\"lazy\" decoding=\"async\" class=\"size-thumbnail wp-image-1001\" src=\"https:\/\/blogs.reed.edu\/chem324\/files\/2015\/02\/BF4-anion-150x150.png\" alt=\"BF4 anion\" width=\"150\" height=\"150\" \/><\/a><figcaption id=\"caption-attachment-1001\" class=\"wp-caption-text\">BF4 anion (EDF2\/6-31G*, iSpartan)<\/figcaption><\/figure>\n","protected":false},"excerpt":{"rendered":"<p>I forget whether this question came up in our discussion of the Scholz paper (paper #1), but 2-norbonyl cation was crystallized with Al2Br7 anion. The authors described this anion as &#8220;weakly coordinating,&#8221; Our interest in binding challenging ions such as the [CX3]+ (X = Cl, Br, or I) cations (35\u201337) to weakly coordinating anions (38, [&hellip;]<\/p>\n","protected":false},"author":55,"featured_media":0,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[5,6],"tags":[],"class_list":["post-999","post","type-post","status-publish","format-standard","hentry","category-molecular-modeling","category-papers-for-discussion"],"_links":{"self":[{"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/posts\/999","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/users\/55"}],"replies":[{"embeddable":true,"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/comments?post=999"}],"version-history":[{"count":4,"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/posts\/999\/revisions"}],"predecessor-version":[{"id":1005,"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/posts\/999\/revisions\/1005"}],"wp:attachment":[{"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/media?parent=999"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/categories?post=999"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/blogs.reed.edu\/chem324\/wp-json\/wp\/v2\/tags?post=999"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}