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Upon reacting SeCl4 with Me3Si–F–Al(ORF)3, the selenonium salt SeMeCl2[al‐f‐al] (1) {[al‐f‐al]– = [F[Al(OC(CF3)3)3]2]–} was obtained and characterized by NMR, IR, and Raman spectroscopy as well as single crystal XRD experiments. Despite the [SeX3]+ (X = F, Cl, Br, I) and [SeR3]+ salts (R = aliphatic organic residue) being well known and thoroughly studied, the mixed cations are scarce. The only previous example of a salt with the [SeMeCl2]+ cation is SeMeCl2[SbCl6], which was never structurally characterized and is unstable in solution over hours. Only 1H‐NMR studies and IR spectra of this compound are known. The unexpected use of Me3Si–F–Al(ORF)3 as a methylating agent was investigated via DFT calculations and NMR experiments of the reaction solution. The reaction of SeCl3[al‐f‐al] with Me3Si‐Cl at room temperature in CH2Cl2 proved to yield the same product with Me3Si–Cl acting as a methylating agent. [ABSTRACT FROM AUTHOR]

Upon reacting SeCl4 with Me3Si–F–Al(ORF)3, the selenonium salt SeMeCl2[al‐f‐al] (1) {[al‐f‐al]– = [F[Al(OC(CF3)3)3]2]–} was obtained and characterized by NMR, IR, and Raman spectroscopy as well as single crystal XRD experiments. Despite the [SeX3]+ (X = F, Cl, Br, I) and [SeR3]+ salts (R = aliphatic organic residue) being well known and thoroughly studied, the mixed cations are scarce. The only previous example of a salt with the [SeMeCl2]+ cation is SeMeCl2[SbCl6], which was never structurally characterized and is unstable in solution over hours. Only 1H‐NMR studies and IR spectra of this compound are known. The unexpected use of Me3Si–F–Al(ORF)3 as a methylating agent was investigated via DFT calculations and NMR experiments of the reaction solution. The reaction of SeCl3[al‐f‐al] with Me3Si‐Cl at room temperature in CH2Cl2 proved to yield the same product with Me3Si–Cl acting as a methylating agent. [ABSTRACT FROM AUTHOR]

To provide a better understanding of the recently published pure metalorganic NiI species, [Ni(cod)2][Al(ORF)4] (1) [cod = 1,5- cyclooctadiene, RF = C(CF3)3], further characterizations were performed and analyzed. Thus, the solvation of 1 in THF was examined by EPR, surprisingly disclosing the initiation of a disproportionation reaction to [NiII(THF)6][Al(ORF)4]2 (3) and Ni0. Further studies con- cerning the ability of 1 to activate small molecules exhibit the formation of a remarkable [Ni3S2(cod)3]2+ cluster (5) in an oxidation reaction with S8, while EPR measurements of the resulting product in a reaction with oxygen indicate a possible coordination of O2. Single crystal X-ray structures as well as spectroscopic analyses of 3 and 5 are described. [ABSTRACT FROM AUTHOR]