%0 Journal Article %T Trimetallic Cubane-Type Clusters Transition-Metal Variation as a Probe of the Roots of Hypoelectronic Metallaheteroboranes %+ Indian Institute of Technology Madras (IIT Madras) %+ Institut des Sciences Chimiques de Rennes (ISCR) %A Kar, Sourav %A Saha, Koushik %A Saha, Suvam %A Kirubakaran, Bakthavachalam %A Dorcet, Vincent %A Ghosh, Sundargopal %Z Council of Scientific and Industrial Research, India %Z Indian Institute of Technology Madras %Z PDF/2016/003998, Science and Engineering Research Board %< avec comité de lecture %@ 0020-1669 %J Inorganic Chemistry %I American Chemical Society %V 57 %N 17 %P 10896–10905 %8 2018 %D 2018 %R 10.1021/acs.inorgchem.8b01531 %M 30124293 %K metallaheteroborane %K adamantane %K thioborate %Z Chemical Sciences/Inorganic chemistry %Z Chemical Sciences/Material chemistryJournal articles %X 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. %G English %2 https://univ-rennes.hal.science/hal-01862463/document %2 https://univ-rennes.hal.science/hal-01862463/file/Kar_Trimetallic%20Cubane-Type%20Clusters.pdf %L hal-01862463 %U https://univ-rennes.hal.science/hal-01862463 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ STATS-UR1 %~ UR1-SPM %~ ISCR-PRATS %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ TEST-HALCNRS %~ UR1-MMS %~ TEST2-HALCNRS %~ TEST3-HALCNRS