Proton and Hydride Affinities in Excited States: Magnitude Reversals in Proton and Hydride Affinities between the Lowest Singlet and Triplet States of Annulenyl and Benzannulenyl Anions and Cations
2010 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 75, no 7, 2189-2196 p.Article in journal (Refereed) Published
Aromaticity has importance for proton and hydride affinities in the singlet ground state (S-0) of annulenyl anions and cations so that, e.g., cyclopentadiene is an acidic hydrocarbon. For the lowest pi pi* excited triplet state (T-1), Baird's rule concludes that annulenes with 4n pi-electrons are aromatic and those with 4n+2 pi-electrons are antiaromatic, opposite to Huckel's rule for aromaticity in S-0. Our hypothesis is now that the relative magnitudes of proton and hydride affinities of annulenyl anions and cations reverts systematically as One goes front S-0 to T-1 as a result of the opposite electron counting rules for aromaticity in the two states. Using quantum Chemical calculations at the G3(MP2)//(U)B3LYP/6-311+G(d,p) level We have examined the validity of this hypothesis for eight proton and eight hydride addition reactions of anions and cations, respectively, of annulenyl and benzannulenyl type. We categorize the (4n+2)pi-electron systems in S-0 and the 4n pi-electron systems in T, to be of A-character and 4n pi-electron systems in S-0 and (4n+2)pi-electron systems in T-1 to be of AA-character (A, aromatic, AA, anti/nonaromatic). The average proton affinities of anions of A- and AA-characters in S-0 are 1447 and 1521 kJ/mol, respectively, and in T-1 they are 1365 and 1493 kJ/mol. The average hydride affinities of A- and AA-character cations in S-0 are 826 and 996 kJ/mol, and in T-1 they are 790 and 879 kJ/mol, respectively. Thus, the calculated proton and hydride affinities are in general lower For anions and cations of A-character than for those of AA-character, in good Support Of Our hypothesis. The findings could likely be applied in synthetic organic photochemistry and other areas where excited state acid-base chemistry plays a role.
Place, publisher, year, edition, pages
2010. Vol. 75, no 7, 2189-2196 p.
IdentifiersURN: urn:nbn:se:uu:diva-136648DOI: 10.1021/jo9025868ISI: 000275884400006PubMedID: 20205444OAI: oai:DiVA.org:uu-136648DiVA: diva2:377328