Dodecamethylcarba-closo-dodecaboranyl (CB₁₁Me₁₂^•), a Stable Free Radical

A Camouflagednido-Carborane Anion: Facile Synthesis of Octa-B-methyl-1,2-dicarba-closo-dodecaborane(12) and Its Deboration Reaction

“…[8] The isolation of the stable radical CB 11 Me 12 . derived from the oxidation of 5 [9] serves as evidence for the stabilizing effect attributed to methyl substitution of the cage. In addition to enhanced stability, these camouflaged carboranes are hydrophobic and exhibit excellent solubility characteristics in common organic solvents.…”

Stable Cubic Phosphorus‐Containing Radicals

“…Examples of stable neutral radicals are less common, but several have been structurally characterized recently in the solid state by X-ray crystallography, for example, CB 11 Me 12 C, [3] [M(dbdab) 2 ] (M = Al, Ga; dbdab = 1,4-di-tertbutyl-1,4-diazabutadiene), [4] [R 2 MMR]C (M = Ga, Al; R = SitBu 3 ), [5][6][7] R 3 SiSi(tBu) 2 C [R = SiMe(tBu) 2 ], [8] [R 3 E]C (E = Si, Ge; R = SiMe(tBu) 2 ), [9] and [Ge(C 6 H 3 Mes 2 -2,6)]C (Mes = 2,4,6-(CH 3 ) 3 C 6 H 2 ). [10] The structure of the phosphorus-centered radical DP[CH(SiMe 3 ) 2 ] 2 C has been determined in the gas phase by electron diffraction.…”

“…[17] However, no reactions of this important member of the family of p-block polyimido anions have been reported. Our recent discovery of a simple and versatile route to tetrakisimidophosphates, for example, [{Li 3 [P(NtBu) 3 -(NSiMe 3 )]} 2 ] (1), [18] has facilitated investigations of the chemistry of these isoelectronic analogues of the orthophosphate PO 4 3À ion. We describe here the synthesis of the stable, neutral radicals [Me 3 SiNP(m 3 -NtBu) 3 {m 3 -Li(thf)} 3 X]C (2 a, X = Br; 2 b, X = I) obtained by the oxidation of 1 with halogens.…”

“…[15] as evidenced by several contacts between iodine and THF hydrogen atoms that are less than the sum of the van der Waals radii. The blue, paramagnetic complex 2 b is comprised of the radical dianion [P(NtBu) 3 2.08 (LiÀN), and 2.75 (LiÀI). The LiÀI bond length is % 0.19 shorter than the corresponding bond in the analogous sulfur(iv) complex.…”

“…Confirmation of the dissociation of the cube was provided by the isolation of the by-product (thf) 3 LiI, which was identified by determination of the unit-cell parameters. [20] We have probed possible structures for the radical monoanion in 3 by using AM1 calculations on the corresponding dianion.…”