{"data":{"id":"10.6084/m9.figshare.c.2185903.v1","type":"dois","attributes":{"doi":"10.6084/m9.figshare.c.2185903.v1","prefix":"10.6084","suffix":"m9.figshare.c.2185903.v1","identifiers":[],"alternateIdentifiers":[],"creators":[{"name":"Domingo, Luis R.","nameType":"Personal","givenName":"Luis R.","familyName":"Domingo","affiliation":[],"nameIdentifiers":[]},{"name":"Ríos-Gutiérrez, Mar","nameType":"Personal","givenName":"Mar","familyName":"Ríos-Gutiérrez","affiliation":[],"nameIdentifiers":[]},{"name":"Pérez, Patricia","nameType":"Personal","givenName":"Patricia","familyName":"Pérez","affiliation":[],"nameIdentifiers":[]},{"name":"Chamorro, Eduardo","nameType":"Personal","givenName":"Eduardo","familyName":"Chamorro","affiliation":[],"nameIdentifiers":[]}],"titles":[{"title":"Understanding the [2n+2n] reaction mechanism between a carbenoid intermediate and CO\u003csub\u003e2\u003c/sub\u003e"}],"publisher":"Figshare","container":{},"publicationYear":2016,"subjects":[{"subject":"Biophysics"},{"subject":"Biochemistry"},{"subject":"29999 Physical Sciences not elsewhere classified","subjectScheme":"FOR"},{"subject":"FOS: Physical sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Physical sciences","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"Cell Biology"},{"subject":"Genetics"},{"subject":"FOS: Biological sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Biological sciences","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"Molecular Biology"},{"subject":"Biotechnology"},{"subject":"Evolutionary Biology"},{"subject":"39999 Chemical Sciences not elsewhere classified","subjectScheme":"FOR"},{"subject":"FOS: Chemical sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Chemical sciences","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"69999 Biological Sciences not elsewhere classified","subjectScheme":"FOR"},{"subject":"Developmental Biology"},{"subject":"Infectious Diseases"},{"subject":"FOS: Health sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Health sciences","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"Computational Biology"}],"contributors":[],"dates":[{"date":"2016-02-09","dateType":"Created"},{"date":"2016-06-02","dateType":"Updated"},{"date":"2016","dateType":"Issued"}],"language":null,"types":{"ris":"GEN","bibtex":"misc","citeproc":"article","schemaOrg":"Collection","resourceType":"Collection","resourceTypeGeneral":"Collection"},"relatedIdentifiers":[{"relationType":"IsSupplementTo","relatedIdentifier":"10.1080/00268976.2016.1142127","relatedIdentifierType":"DOI"},{"relationType":"IsIdenticalTo","relatedIdentifier":"10.6084/m9.figshare.c.2185903","relatedIdentifierType":"DOI"}],"relatedItems":[],"sizes":[],"formats":[],"version":null,"rightsList":[{"rights":"CC-BY","rightsUri":"http://creativecommons.org/licenses/by/3.0/us"}],"descriptions":[{"description":"The mechanism of the cycloaddition reaction of CO\u003csub\u003e2\u003c/sub\u003e with a nucleophilic carbenoid intermediate has been theoretically studied by using the bonding evolution theory (BET) at the B3LYP/6-31G(d) level of theory. BET combines topological analysis of the electron localisation function and catastrophe theory along a reaction path. This cycloaddition reaction is characterised by 16 structural stability domains, associated to the following sequence of catastrophes: C\u003csub\u003e8\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003eNO\u003csub\u003e4\u003c/sub\u003e + CO\u003csub\u003e2\u003c/sub\u003e: 16-CF\u003csup\u003e†\u003c/sup\u003eCF\u003csup\u003e†\u003c/sup\u003eF\u003csup\u003e†\u003c/sup\u003eCFF\u003csup\u003e†\u003c/sup\u003eC\u003csup\u003e†\u003c/sup\u003eC\u003csup\u003e†\u003c/sup\u003e[FF\u003csup\u003e†\u003c/sup\u003e]F\u003csup\u003e†\u003c/sup\u003eFCC\u003csup\u003e†\u003c/sup\u003e-0: C\u003csub\u003e9\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003eNO\u003csub\u003e6\u003c/sub\u003e. Formation of the two new C-C and C-O single bonds evolves after the transition state structure is reached. The high nucleophilic character and the electronic structure of carbenoid intermediate together with the specific approaching mode of the CO\u003csub\u003e2\u003c/sub\u003e molecule enable in fact the first C-C single bond formation after a very low activation enthalpy, 2.2 kcal/mol, without any external electrophilic activation. The subsequent ring closure via formation of the C-O single bond occurs at the end of the reaction. We propose thereafter a rationalisation of such a \u003ci\u003epolar reaction process\u003c/i\u003e in terms of a [2n+2n] cycloaddition reaction following a non-concerted \u003ci\u003etwo-stage one-step mechanism\u003c/i\u003e, in contrast to the simplified picture of rationalisation traditionally based on molecular orbitals.","descriptionType":"Abstract"}],"geoLocations":[],"fundingReferences":[],"xml":"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