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Trimetallic Cubane-Type Clusters: Transition-Metal Variation as a Probe of the Roots of Hypoelectronic Metallaheteroboranes
Sourav Kar, Koushik Saha, Suvam Saha, Bakthavachalam Kirubakaran,
Published in American Chemical Society
Volume: 57
Issue: 17
Pages: 10896 - 10905
In an effort to synthesize chalcogen-rich metallaheteroborane clusters of group 5 metals, thermolysis of [Cp∗TaCl4] (Cp∗ = n5-C5Me5) with thioborate ligand Li[BH2S3] was carried out, affording trimetallic clusters [(Cp∗Ta)3(μ-S)3(μ3-S)3B(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)4(μ-S)6(μ3-S)(μ4-O)], 6, having an adamantane core structure. Compound 6 is one of the rarest examples containing the μ4-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)3(μ-Se)3(μ3-Se)3B(H)], 4, from the thermolytic reaction of [Cp∗TaCl4] and Li[BH2Se3]. In contrast, the thermolysis of [Cp∗TaCl4] with Li[BH2Te3] under the same reaction conditions yielded tantalum telluride complex [(Cp∗Ta)2(μ-Te)2], 5. Compounds 1-4 are hypo-electronic clusters with an electron count of 50 cluster valence electrons. All these compounds have been characterized by 1H, 11B{1H}, and 13C{1H} 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. Copyright © 2018 American Chemical Society.
About the journal
JournalData powered by TypesetInorganic Chemistry
PublisherData powered by TypesetAmerican Chemical Society
Open AccessYes