Preparation of an ion with the highest calculated proton affinity:: Ortho -diethynylbenzene dianion (2024)

Poad, B. L. J., Reed, N. D., Hansen, C. S., Trevitt, A. J., Blanksby, S. J., Mackay, E. G., Sherburn, M. S., Chan, B., & Radom, L. (2016). Preparation of an ion with the highest calculated proton affinity:: Ortho -diethynylbenzene dianion. Chemical Science, 7(9), 6245-6250. https://doi.org/10.1039/c6sc01726f

Poad, Berwyck L.J. ; Reed, Nicholas D. ; Hansen, Christopher S. et al. / Preparation of an ion with the highest calculated proton affinity:: Ortho -diethynylbenzene dianion. In: Chemical Science. 2016 ; Vol. 7, No. 9. pp. 6245-6250.

@article{c14e789e021d4a199bef7aab6e3e3493,

title = "Preparation of an ion with the highest calculated proton affinity:: Ortho -diethynylbenzene dianion",

abstract = "Owing to the increased proton affinity that results from additional negative charges, multiply-charged anions have been proposed as one route to prepare and access a range of new and powerful {"}superbases{"}. Paradoxically, while the additional electrons in polyanions increase basicity they serve to diminish the electron binding energy and thus, it had been thought, hinder experimental synthesis. We report the synthesis and isolation of the ortho-diethynylbenzene dianion (ortho-DEB2-) and present observations of this novel species undergoing gas-phase proton-abstraction reactions. Using a theoretical model based on Marcus-Hush theory, we attribute the stability of ortho-DEB2- to the presence of a barrier that prevents spontaneous electron detachment. The proton affinity of 1843 kJ mol-1 calculated for this dianion superbase using high-level quantum chemistry calculations significantly exceeds that of the lithium monoxide anion, the most basic system previously prepared. The ortho-diethynylbenzene dianion is therefore the strongest base that has been experimentally observed to date.",

author = "Poad, {Berwyck L.J.} and Reed, {Nicholas D.} and Hansen, {Christopher S.} and Trevitt, {Adam J.} and Blanksby, {Stephen J.} and Mackay, {Emily G.} and Sherburn, {Michael S.} and Bun Chan and Leo Radom",

note = "Publisher Copyright: {\textcopyright} 2016 The Royal Society of Chemistry.",

year = "2016",

doi = "10.1039/c6sc01726f",

language = "English",

volume = "7",

pages = "6245--6250",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "9",

}

Poad, BLJ, Reed, ND, Hansen, CS, Trevitt, AJ, Blanksby, SJ, Mackay, EG, Sherburn, MS, Chan, B & Radom, L 2016, 'Preparation of an ion with the highest calculated proton affinity:: Ortho -diethynylbenzene dianion', Chemical Science, vol. 7, no. 9, pp. 6245-6250. https://doi.org/10.1039/c6sc01726f

Preparation of an ion with the highest calculated proton affinity:: Ortho -diethynylbenzene dianion. / Poad, Berwyck L.J.; Reed, Nicholas D.; Hansen, Christopher S. et al.
In: Chemical Science, Vol. 7, No. 9, 2016, p. 6245-6250.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Preparation of an ion with the highest calculated proton affinity:: Ortho -diethynylbenzene dianion

AU - Poad, Berwyck L.J.

AU - Reed, Nicholas D.

AU - Hansen, Christopher S.

AU - Trevitt, Adam J.

AU - Blanksby, Stephen J.

AU - Mackay, Emily G.

AU - Sherburn, Michael S.

AU - Chan, Bun

AU - Radom, Leo

N1 - Publisher Copyright:© 2016 The Royal Society of Chemistry.

PY - 2016

Y1 - 2016

N2 - Owing to the increased proton affinity that results from additional negative charges, multiply-charged anions have been proposed as one route to prepare and access a range of new and powerful "superbases". Paradoxically, while the additional electrons in polyanions increase basicity they serve to diminish the electron binding energy and thus, it had been thought, hinder experimental synthesis. We report the synthesis and isolation of the ortho-diethynylbenzene dianion (ortho-DEB2-) and present observations of this novel species undergoing gas-phase proton-abstraction reactions. Using a theoretical model based on Marcus-Hush theory, we attribute the stability of ortho-DEB2- to the presence of a barrier that prevents spontaneous electron detachment. The proton affinity of 1843 kJ mol-1 calculated for this dianion superbase using high-level quantum chemistry calculations significantly exceeds that of the lithium monoxide anion, the most basic system previously prepared. The ortho-diethynylbenzene dianion is therefore the strongest base that has been experimentally observed to date.

AB - Owing to the increased proton affinity that results from additional negative charges, multiply-charged anions have been proposed as one route to prepare and access a range of new and powerful "superbases". Paradoxically, while the additional electrons in polyanions increase basicity they serve to diminish the electron binding energy and thus, it had been thought, hinder experimental synthesis. We report the synthesis and isolation of the ortho-diethynylbenzene dianion (ortho-DEB2-) and present observations of this novel species undergoing gas-phase proton-abstraction reactions. Using a theoretical model based on Marcus-Hush theory, we attribute the stability of ortho-DEB2- to the presence of a barrier that prevents spontaneous electron detachment. The proton affinity of 1843 kJ mol-1 calculated for this dianion superbase using high-level quantum chemistry calculations significantly exceeds that of the lithium monoxide anion, the most basic system previously prepared. The ortho-diethynylbenzene dianion is therefore the strongest base that has been experimentally observed to date.

UR - http://www.scopus.com/inward/record.url?scp=84983456976&partnerID=8YFLogxK

U2 - 10.1039/c6sc01726f

DO - 10.1039/c6sc01726f

M3 - Article

SN - 2041-6520

VL - 7

SP - 6245

EP - 6250

JO - Chemical Science

JF - Chemical Science

IS - 9

ER -

Poad BLJ, Reed ND, Hansen CS, Trevitt AJ, Blanksby SJ, Mackay EG et al. Preparation of an ion with the highest calculated proton affinity:: Ortho -diethynylbenzene dianion. Chemical Science. 2016;7(9):6245-6250. doi: 10.1039/c6sc01726f