Single-Not Double-3D-Aromaticity in an Oxidized Closo Icosahedral Dodecaiodo-Dodecaborate Cluster

Poater, JordiUniv Barcelona, Dept Quim Inorgan & Organ, Barcelona 08028, Spain.;Univ Barcelona, IQTCUB, Barcelona 08028, Spain.;ICREA, Pg Lluis Co 23, Barcelona 08010, Spain. (författare)

3D-aromatic molecules with (distorted) tetrahedral, octahedral, or spherical structures are much less common than typical 2D-aromatic species or even 2D-aromatic-in-3D systems. Closo boranes, [BnHn](2-) (5 = n = 14) and carboranes are examples of compounds that are singly 3D-aromatic, and we now explore if there are species that are doubly 3D-aromatic. The most widely known example of a species with double 2D-aromaticity is the hexaiodobenzene dication, [C6I6](2+). This species shows p-aromaticity in the benzene ring and s-aromaticity in the outer ring formed by the iodine substituents. Inspired by the hexaiodobenzene dication example, in this work, we explore the potential for double 3D-aromaticity in [B12I12](0/2+). Our results based on magnetic and electronic descriptors of aromaticity together with B-11{H-1} NMR experimental spectra of boron-iodinated o-carboranes suggest that these two oxidized forms of a closo icosahedral dodecaiodo-dodecaborate cluster, [B12I12] and [B12I12](2+), behave as doubly 3D-aromatic compounds. However, an evaluation of the energetic contribution of the potential double 3D-aromaticity through homodesmotic reactions shows that delocalization in the I-12 shell, in contrast to the 10s-electron I-6(2+) ring in the hexaiodobenzene dication, does not contribute to any stabilization of the system. Therefore, the [B12I12](0/2+) species cannot be considered as doubly 3D-aromatic.

Escayola, SilviaUniv Girona, Inst Quim Computac & Catalisi, Dept Quim, Girona 17003, Spain.;Donostia Int Phys Ctr DIPC, Euskadi 20018, Spain. (författare)
Poater, AlbertUniv Girona, Inst Quim Computac & Catalisi, Dept Quim, Girona 17003, Spain. (författare)
Teixidor, FrancescCampus Univ Autonoma Barcelona, CSIC, Inst Cie`ncia Mat Barcelona, Bellaterra 08193, Spain. (författare)
Ottosson, HenrikUppsala universitet,Institutionen för kemi - Ångström(Swepub:uu)heott255 (författare)
Vinas, ClaraCampus Univ Autonoma Barcelona, CSIC, Inst Cie`ncia Mat Barcelona, Bellaterra 08193, Spain. (författare)
Sola, MiquelUniv Girona, Inst Quim Computac & Catalisi, Dept Quim, Girona 17003, Spain. (författare)
Univ Barcelona, Dept Quim Inorgan & Organ, Barcelona 08028, Spain.;Univ Barcelona, IQTCUB, Barcelona 08028, Spain.;ICREA, Pg Lluis Co 23, Barcelona 08010, Spain.Univ Girona, Inst Quim Computac & Catalisi, Dept Quim, Girona 17003, Spain.;Donostia Int Phys Ctr DIPC, Euskadi 20018, Spain. (creator_code:org_t)

Ingår i:Journal of the American Chemical Society: American Chemical Society (ACS)145:41, s. 22527-225380002-78631520-5126

Av författaren/redakt...: Poater, Jordi; Escayola, Silvia; Poater, Albert; Teixidor, France ...; Ottosson, Henrik; Vinas, Clara; visa fler...; Sola, Miquel; visa färre...

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