Reaktionen von Trimethylstiban in den supersauren Systemen XF/MF5 (X = H, D; M = As, Sb), Kristallstrukturen von (CH3)3SbD+SbF6- und (CH3)3SbSb(CH3)32+(SbF6-)2 · SO2

Chlorine/Methyl Exchange Reactions in Silylated Aminostibanes: A New Route To Stibinostibonium Cations

“…Only three classes are known: (i) [R 3 Sb–(SbR) n –SbR 2 ] + , (ii) [R 2 Sb–(SbR) n –SbR 2 –(SbR) n –SbR 2 ] + , and one dicationic series (iii) [R 3 Sb–(SbR) n –SbR 3 ] 2+ ( n = 0, 1, 2, etc.). [Me 3 Sb–SbMe 2 ] + as [GaCl 4 ] − ( 9 ) and [MeSbBr 3 ] − salt belong to the [R 3 Sb–(SbR) n –SbR 2 ] + series with n = 0, while dication 13 [R 3 Sb–Sb(R)–SbR 3 ] 2+ ( n = 1) represents the next example of the series [R 3 Sb–(SbR) n –SbR 3 ] 2+ for which the parent species [Me 3 Sb–SbMe 3 ] 2+ ( n = 0) was isolated as [SbF 6 ] − salt from the reaction of Me 3 Sb in the super acidic medium HF/SbF 5 by Minkwitz . Furthermore, only the parent species ( n = 0) of the monocationic series [R 2 Sb–(SbR) n –SbR 2 –(SbR) n –SbR 2 ] + has been reported which was characterized as [Me 2 Sb–SbMe 2 –SbMe 2 ][Me 2 SbBr 2 ] …”

“…NMR. 13 C{ 1 H}, 13 C DEPT, 1 H, 19 F{ 1 H}, and 29 Si INEPT NMR spectra were obtained on a Bruker AVANCE 300 spectrometer and were referenced internally to the deuterated solvent ( 13 MS. Finnigan MAT 95-XP from Thermo Electron was used. X-ray Structure Determination.…”

Synthesis and reactivity of cyclo-tetra(stibinophosphonium) tetracations: redox and coordination chemistry of phosphine–antimony complexes

“…14 Examples of cationic homocycles for p-block metalloids are limited to unsupported selenium and tellurium dications 15 and heavily substituted silicon 16 or germanium 17 monocations. For antimony, a number of acyclic catenated monocations ( [1] 1+ and [2] 1+ ) [18][19][20] and dications ([3] 2+ , [4] 2+ , [5] 2+ and [6] 2+ ) 19,[21][22][23] have recently been isolated (Chart 1), but generally on small scales, precluding further reactivity studies of these interesting species. Enabled by a rational and large scale synthetic protocol for cations [10(R)] 4+ , we now report the reaction chemistry of the prototypical derivative, [10(Me)] 4+ , debuting the coordination chemistry of a new catenaelement framework.…”

Phosphinoarsonium and Diarsonium Cations from Chloride-Abstraction-Induced Pnictogen Coupling

“…The eclipsed conformation of the diarsonium cation 6 reveals an As−As bond length [2.4109(3) Å] that is only slightly shorter than that in a neutral diarsine ([MesC(O)] 2 As−As[C(O)Mes] 2 = 2.4300(8) Å) . For comparison, a larger difference is observed between the Sb−Sb bond length in the hexamethyldistibonium dication [2.7624(11) and 2.7867(12) Å] and in tetramethyldistibine [2.862(2), 2.830(1), and 2.838(1) Å] …”