Trimetallic Cubane-Type Clusters Transition-Metal Variation as a Probe of the Roots of Hypoelectronic Metallaheteroboranes - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2018

Trimetallic Cubane-Type Clusters Transition-Metal Variation as a Probe of the Roots of Hypoelectronic Metallaheteroboranes

Résumé

In an effort to synthesize chalcogen-rich metallaheteroborane clusters of group 5 metals, thermolysis of [Cp*TaCl] (Cp* = η-CMe) with thioborate ligand Li[BHS] was carried out, affording trimetallic clusters [(Cp*Ta)(μ-S)(μ-S)B(R)], 1-3 (1, R = H; 2, R = SH; and 3, R = Cl). Clusters 1-3 are illustrative examples of cubane-type organotantalum sulfido clusters in which one of the vertices of the cubane is missing. In parallel to the formation of 1-3, the reaction also yielded tetrametallic sulfido cluster [(Cp*Ta)(μ-S)(μ-S)(μ-O)], 6, having an adamantane core structure. Compound 6 is one of the rarest examples containing the μ-oxo unit with a heavier early transition metal, i.e., tantalum. In an effort to isolate selenium analogues of clusters 1-3, we have isolated the trimetallic cluster [(Cp*Ta)(μ-Se)(μ-Se)B(H)], 4, from the thermolytic reaction of [Cp*TaCl] and Li[BHSe]. In contrast, the thermolysis of [Cp*TaCl] with Li[BHTe] under the same reaction conditions yielded tantalum telluride complex [(Cp*Ta)(μ-Te)], 5. Compounds 1-4 are hypo-electronic clusters with an electron count of 50 cluster valence electrons. All these compounds have been characterized by H, B{H}, and C{H} NMR spectroscopy; infrared spectroscopy; mass spectrometry; and single-crystal X-ray crystallography. The density functional theory calculations were also carried out to provide insight into the bonding and electronic structures of these molecules.
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Dates et versions

hal-01862463 , version 1 (14-09-2018)

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Sourav Kar, Koushik Saha, Suvam Saha, Bakthavachalam Kirubakaran, Vincent Dorcet, et al.. Trimetallic Cubane-Type Clusters Transition-Metal Variation as a Probe of the Roots of Hypoelectronic Metallaheteroboranes. Inorganic Chemistry, 2018, 57 (17), pp.10896-10905. ⟨10.1021/acs.inorgchem.8b01531⟩. ⟨hal-01862463⟩
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