Radical cations from diarylamino-substituted fluorenones

Homnick, Paul J.; Tinkham, Jonathan S.; Lahti, Paul M.

doi:10.1016/j.tetlet.2012.10.060

Cited by 5 publications

References 25 publications

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Long‐Lived Radical Cation Salts Obtained by Interaction of Monocyclic Arenes with Niobium and Tantalum Pentahalides at Room Temperature: EPR and DFT Studies

Marchetti¹,

Pampaloni²,

Pinzino³

2013

Chemistry A European J

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The 1:3 reactions of the alkoxy arenes 1,4-(MeO)2 C6 H4 and 1,4-F2 -2,5-(MeO)2 C6 H2 with TaF5 in chloroform at 40-50 °C resulted in formation in about 35 % yield of the long-lived radical cation salts [1,4-(MeO)2 C6 H4 ][Ta2 F11 ] (2 a) and [1,4-F2 -2,5-(MeO)2 C6 H2 ][Ta2 F11 ] (2 b), respectively. The non-alkoxy-substituted [arene][M2 X11 ] [M=Ta, X=F: arene=C6 H5 Me (2 c), 1,4-C6 H4 Me2 (2 d), C6 H5 F (2 e), C6 H5 NO2 (2 f); M=Nb, X=F: arene=C6 H5 Me (4 a), 1,4-C6 H4 Me2 (4 b), C6 H5 F (4 c), C6 H5 NO2 (4 d); M=Ta, X=Cl: arene=1,4-C6 H4 Me2 (5)] were obtained from the 3:1 reactions of MX5 with the appropriate arene in chloroform at temperatures in the range 40-90 °C. Compounds 2-5 were detected by EPR spectroscopy (in CHCl3 ) at room temperature, and their gas-phase structures were optimized by DFT calculations. Formation of the M(IV) species [MX4 (NCMe)2 ] [M=Ta, X=F (3 a); M=Nb, X=F (3 b); M=Ta, X=Cl (3 c)] was ascertained by EPR spectroscopy on solutions obtained by treatment of the reaction mixtures with acetonitrile. Non-selective reactions occurred upon combination of 1,4-F2 -2,5-(MeO)2 C6 H2 with AgNbF6 (in CH2 Cl2 ) and 1,4-(MeO)2 C6 H4 with SbF5 .

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Long‐Lived Radical Cation Salts Obtained by Interaction of Monocyclic Arenes with Niobium and Tantalum Pentahalides at Room Temperature: EPR and DFT Studies

Marchetti¹,

Pampaloni²,

Pinzino³

2013

Chemistry A European J

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Stable [M₂F₁₁]^– (M = Nb, Ta) Salts of Protonated 1,3‐Dimethoxybenzene

et al. 2013

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The 3:1 molar reactions of MF 5 (M = Nb, 1a; M = Ta, 1b) with 1,3-dimethoxybenzene in CHCl 3 led to the formation of the arenium salts [2,4-(OMe) 2 C 6 H 5 ][M 2 F 11 ] (M = Nb, 3a; M = Ta, 3b) in good yields. The reactions took place with the intermediate formation of (MF 5 ) 2 [κ 2 -1,3-(OMe) 2 C 6 H 4 ] (M = Nb, 2a; M = Ta, 2b), followed by single-electron oxidation of the arene and production of MF 4 (identified by means of EPR spectroscopy as the acetonitrile adduct). Compounds 3a and[a]

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