Collect. Czech. Chem. Commun. 1997, 62, 47-56

Dimethyl Sulfate Induced Nucleophilic Substitution of the [Bis(1,2-dicarbollido)-3-cobalt(1-)]ate Ion. Syntheses, Properties and Structures of Its 8,8'-μ-Sulfato, 8-Phenyland 8-Dioxane Derivatives

Jaromír Plešeka, Stanislav Heřmáneka, Andreas Frankena, Ivana Císařováb and Christiane Nachtigalc

a Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, 250 68 Řež near Prague, Czech Republic
b Department of Inorganic Chemistry, Charles University, 128 40 Prague 2, Czech Republic
c Christian Albrecht University, 24098 Kiel, Germany


Syntheses and structures of [8,8'-μ-(OSO2O)(1,2-C2B9H10)2-3-Co]-and [(8-Ph-1,2-C2B9H10)-3-Co-(1',2'-C2B9H11]- ions and of [(8-dioxane-1,2-C2B9H10)-3-Co-(1',2'-C2B9H11)] zwitterion are described. All compounds result on dimethyl sulfate induced nucleophilic B-substitution of the parent cobalta-carborane sandwich ion under acid catalysis. A general mechanism is proposed. Constitutions of all compounds are inferred from the mass and multinuclear NMR spectroscopy and all structures are established by X-ray diffraction. Selected NMR and X-ray data are presented.

Keywords: Electrophile induced nucleophilic substitutions; Cobaltacarborane sandwich complexes; X-Ray structures; Multinuclear NMR; -OSO2O- bridge.