{"id":10498,"date":"2013-05-15T20:01:40","date_gmt":"2013-05-15T19:01:40","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=10498"},"modified":"2014-01-17T07:46:06","modified_gmt":"2014-01-17T07:46:06","slug":"au-and-pt-%cf%80-complexes-of-cyclobutadiene","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498","title":{"rendered":"Au and Pt \u03c0-complexes of cyclobutadiene."},"content":{"rendered":"
\n

In the preceding post<\/a>, I introduced Dewar’s\u00a0\u03c0-complex theory for alkene-metal compounds, outlining the molecular orbital analysis he presented, in which the filled \u03c0-MO of the alkene donates into a Ag+<\/sup>\u00a0empty metal orbital and back-donation occurs from a filled metal orbital into the alkene \u03c0* MO. Here I play a little “what if” game with this scenario to see what one can learn from doing so.<\/p>\n

\"Au+cbd\"<\/p>\n

Firstly, I will use Au+<\/sup> instead of Ag+<\/sup>, so as to make a comparison with Pt2+<\/sup> a little more direct. The electronic configurations are of course\u00a0[Xe].4f14<\/sup>.5d10<\/sup>.6s0<\/sup>\u00a0and\u00a0[Xe].4f14<\/sup>.5d8<\/sup>.6s0<\/sup> respectively. I will also replace a simple ethene with cyclobutadiene, the intent here being that this cyclo-diene is a very much better\u00a0\u03c0-donor due to its anti-aromatic character. It also now has the possibility of acting as a four or a two-electron donor. I started with M=Pt+<\/sup>[1]<\/a><\/span> by adding another double bond to the structure of the ethene complex.\u00a0<\/p>\n

\"Pt-cbd\"<\/p>\n

Optimising this starting structure in fact moves the metal and the final geometry has C4v<\/sub> symmetry; in other words the metal is bound symmetrically to all four carbons. The four C-C lengths are all the same (1.46\u00c5) and strongly suggest that four electrons from the cyclobutadiene are participating in bonding; the Pt2+<\/sup> is clearly capable of accepting four electrons, two into 6s0\u00a0<\/sup>and two into\u00a05d8<\/sup>. In the process, the cyclobutadiene looses its antiaromaticity. The molecular orbitals of this species are all lovely; I illustrate just one below.<\/p>\n

\"Click

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

If the Pt in this C4v<\/sub> structure is mutated into Au+<\/sup>, the resulting optimised stationary point exhibits a negative force constant characteristic of a transition state[2]<\/a><\/span>. As the d-shell is already fully, the Au can only accept two electrons, and this is therefore a nice illustration of the “18-electron” rule in operation. So, the Au+<\/sup> complex must exist in at least one lower energy form. For example, one where the Au+<\/sup> is coordinated to only one alkene is 94 kcal\/mol lower in free energy.[3]<\/a><\/span> This form results in electrons from the coordinated alkene being donated into the 6s Au orbital, and this action reduces the anti-aromaticity of the cyclobutadiene ring.<\/p>\n

\"Au-cs\"<\/p>\n

Another isomer also achieves this result, resulting in a further lowering in free energy of 11.0 kcal\/mol[4]<\/a><\/span> The anti-aromaticity this time is eliminated by forming an allyl cation on the ring. I have described this mode in another post<\/a>, commenting on the effect when a guanidinium cation interacts with cyclobutadiene.\"Au-cs1\"<\/p>\n

We have learnt that cyclobutadiene has many modes for eliminating 4n-electron antiaromaticity and other destabilising influences upon the ring. It can accept four electrons from a suitable acceptor (Pt2+<\/sup>), or two electrons from Au+<\/sup> in two different ways.<\/p>\n

References<\/h2>\n
  1. H.S. Rzepa, \"Gaussian Job Archive for C4H4Pt(2+)\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.703546<\/a>\n\n<\/li>\n
  2. H.S. Rzepa, \"Gaussian Job Archive for C4H4Au(1+)\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.703547<\/a>\n\n<\/li>\n
  3. H.S. Rzepa, \"Gaussian Job Archive for C4H4Au(1+)\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.703576<\/a>\n\n<\/li>\n
  4. H.S. Rzepa, \"Gaussian Job Archive for C4H4Au(1+)\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.703577<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    In the preceding post, I introduced Dewar’s\u00a0\u03c0-complex theory for alkene-metal compounds, outlining the molecular orbital analysis he presented, in which the filled \u03c0-MO of the alkene donates into a Ag+\u00a0empty metal orbital and back-donation occurs from a filled metal orbital into the alkene \u03c0* MO. Here I play a little “what if” game with this […]<\/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":[7,4],"tags":[1060,1064,1063,24,1061,40,2651,1062,157],"ppma_author":[2661],"class_list":["post-10498","post","type-post","status-publish","format-standard","hentry","category-hypervalency","category-interesting-chemistry","tag-african-union","tag-alkene-metal-compounds","tag-empty-metal-orbital","tag-energy","tag-filled-metal-orbital","tag-free-energy","tag-historical","tag-lower-energy-form","tag-metal"],"yoast_head":"\nAu and Pt \u03c0-complexes of cyclobutadiene. - 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=10498\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Au and Pt \u03c0-complexes of cyclobutadiene. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"In the preceding post, I introduced Dewar’s\u00a0\u03c0-complex theory for alkene-metal compounds, outlining the molecular orbital analysis he presented, in which the filled \u03c0-MO of the alkene donates into a Ag+\u00a0empty metal orbital and back-donation occurs from a filled metal orbital into the alkene \u03c0* MO. Here I play a little “what if” game with this […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2013-05-15T19:01:40+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2014-01-17T07:46:06+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/Au+cbd.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=\"2 minutes\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Au and Pt \u03c0-complexes of cyclobutadiene. - Henry Rzepa's Blog","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498","og_locale":"en_GB","og_type":"article","og_title":"Au and Pt \u03c0-complexes of cyclobutadiene. - Henry Rzepa's Blog","og_description":"In the preceding post, I introduced Dewar’s\u00a0\u03c0-complex theory for alkene-metal compounds, outlining the molecular orbital analysis he presented, in which the filled \u03c0-MO of the alkene donates into a Ag+\u00a0empty metal orbital and back-donation occurs from a filled metal orbital into the alkene \u03c0* MO. Here I play a little “what if” game with this […]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498","og_site_name":"Henry Rzepa's Blog","article_published_time":"2013-05-15T19:01:40+00:00","article_modified_time":"2014-01-17T07:46:06+00:00","og_image":[{"url":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/Au+cbd.svg","type":"","width":"","height":""}],"author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"2 minutes"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"Au and Pt \u03c0-complexes of cyclobutadiene.","datePublished":"2013-05-15T19:01:40+00:00","dateModified":"2014-01-17T07:46:06+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498"},"wordCount":481,"commentCount":1,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/Au+cbd.svg","keywords":["African Union","alkene-metal compounds","empty metal orbital","energy","filled metal orbital","free energy","Historical","lower energy form","metal"],"articleSection":["Hypervalency","Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10498","name":"Au and Pt \u03c0-complexes of cyclobutadiene. - 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In\u00a0\"A review of \u03c0 Complex Theory\",\u00a0 Bull. Soc. Chim. Fr., 1951, 1 8 , C79 (it is not online) M. J. S.\u00a0Dewar\u00a0sets out\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":16518,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=16518","url_meta":{"origin":10498,"position":1},"title":"A wider look at \u03c0-complex metal-alkene (and alkyne) compounds.","author":"Henry Rzepa","date":"June 13, 2016","format":false,"excerpt":"Previously, I looked at the historic origins of the so-called \u03c0-complex theory of metal-alkene complexes. Here I follow this up with some data mining of the crystal structure database for such structures. Alkene-metal \"\u03c0-complexes\" have what might be called a representational problem; they do not happily fit into the standard\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":26812,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=26812","url_meta":{"origin":10498,"position":2},"title":"Mechanistic templates computed for the Grubbs alkene-metathesis reaction.","author":"Henry Rzepa","date":"February 19, 2024","format":false,"excerpt":"Following on from my template exploration of the Wilkinson hydrogenation catalyst, I now repeat this for the Grubbs variant of the Alkene metathesis reaction. As with the Wilkinson, here I focus on the stereochemistry of the mechanism as first suggested by Chauvin, an aspect lacking in eg the Wikipedia entry.\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":8216,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8216","url_meta":{"origin":10498,"position":3},"title":"Secrets revealed for conjugate addition to cyclohexenone using a Cu-alkyl reagent.","author":"Henry Rzepa","date":"November 4, 2012","format":false,"excerpt":"The text books say that cyclohexenone A will react with a Grignard reagent by delivery of an alkyl (anion) to the carbon of the carbonyl (1,2-addition) but if dimethyl lithium cuprate is used, a conjugate 1,4-addition proceeds, to give the product B shown below. The standard explanation is that the\u2026","rel":"","context":"In \"metal\"","block_context":{"text":"metal","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=metal"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/11\/4.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":8925,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8925","url_meta":{"origin":10498,"position":4},"title":"\u03c0-hydrogen bonds as a function of ring size.","author":"Henry Rzepa","date":"January 5, 2013","format":false,"excerpt":"A simple correlation between a ring size and the hydrogen bonding as quantified by the O(Lp)\/H-O \u03c3* NBO interaction in that ring,\u00a0indicated a 7- or 8-membered ring was preferred over smaller ones. Here is the same study, but this time using the \u03c0-electrons of an alkene as the electron donor.\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":"WAK","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/WAK.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":5040,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5040","url_meta":{"origin":10498,"position":5},"title":"Are close H\u2026H contacts bonds? The d\u00e9nouement!","author":"Henry Rzepa","date":"October 10, 2011","format":false,"excerpt":"I wrote earlier about the strangely close contact between two hydrogen atoms in cis-butene. The topology of the electron density showed characteristics of a bond, but is it a consensual union? The two hydrogens approach closer than their van der Waals radii would suggest is normal, so something is happening,\u2026","rel":"","context":"In "General"","block_context":{"text":"General","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/10\/cis-butene-C-H.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\/10498","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=10498"}],"version-history":[{"count":13,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/10498\/revisions"}],"predecessor-version":[{"id":11943,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/10498\/revisions\/11943"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=10498"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=10498"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=10498"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=10498"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}