Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 75, Issue 4, Pages 1168-1178Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo902411b
Keywords
-
Categories
Funding
- ESPRC
- U.S. National Science Foundation [CHE-0715375]
- EPSRC [EP/E052142/1] Funding Source: UKRI
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0948606] Funding Source: National Science Foundation
- Engineering and Physical Sciences Research Council [EP/E052142/1] Funding Source: researchfish
Ask authors/readers for more resources
Three 3,6-difluoro-1,2,4,5-tetrakis(amino)benzene compounds, bearing dimethylamino (1), piperidin-1-yl (3), or morpholin-1-yl (5) substituents, have been synthesized and subsequently defluorinated to give the corresponding 1,2,4,5-tetrakis(amino)benzene compounds 2, 4, and 6; the crystal structures of compounds 1, 4, and 6 have been obtained. Cyclic voltammetry shows that all six compounds will lose two electrons to form dications, and the use of suitable oxidizing agents has allowed isolation and crystallographic characterization of the dications 2(2+) and 6(2+) (as [PF(6)](2) salts) and 4(2+) (as a [I(5)][I(3)] salt). The separation Delta E between the loss of the first electron and the second varies between compounds, from 0.23 V in 1 to 0.01 V in 6. Eletrochemical studies involving the use of the noncoordinating electrolyte [Bu(4)N][B{C(6)H(3)(CF(3))(2)}(4)] show that it is possible to increase this separation, stabilizing the intermediate monocationic phase, and this has allowed the isolation and crystallographic characterization of the radical salts 2[B{C(6)H(3)(CF(3))(2)}(4)] and 4[B{C(6)H(3)(CF(3))(2)}(4)], the first radical cations of this family to be isolated. DFT studies or the ion pairing between oxidized forms of 1 and 2 and anions imply that the location of the ion pairing is different in the two species.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available