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Article Dans Une Revue Journal of Organometallic Chemistry Année : 2024

Syntheses, Structures, and Bonding of Boron Containing Niobium and Ruthenium Clusters Stabilized by Chalcogens

Résumé

In an effort to synthesize niobaheteroboranes and ruthenaheteroboranes, two different synthetic methods are developed. The reactions of [Cp*NbCl4] (1) with chalcogenaborate ligands [LiBH2E3] (E = S, Se) were carried out under reflux conditions. The reaction with sulfur yielded a triniobium polysulfide cluster [(Cp*Nb)3(μ3-S)3{B(OCH3)}(μ-S)3] (2) in which a trithiaborate ligand [S3B(OCH3)]− is coordinated to Nb3 framework in a cubane-type geometry. While the reaction with selenium generated a diniobium polyselenide cluster [(Cp*NbCl)2(μ-Se2-κ1Se:κ2Se')2(μ-O)] (3) in which two diselenide ligands {[Se2]2−} are coordinated with both the metal centres in an unsymmetrical κ1:κ2 fashion. On the other hand, efforts were directed towards expliciting the coordinative sulfur centres of a preformed arachno‑ruthenaborane [(Cp*Ru)2(B3H8)(CS2H)] (arachno‑4), by carrying out the pyrolysis of arachno‑4 with excess [BH3⋅THF]. The reaction led to the formation of sulfido stabilized pileo cluster nido‑ruthenathiaborane [2,3-(Cp*Ru)2(μ-H)(B3H6)S] (5), nido‑ruthenaborane [2,3-(Cp*Ru)2(μ-H)(B4H5Me)] (6) and thiomethyl bridged nido‑ruthenaborane [2,3-(Cp*Ru)2(μ-SMe)(B3H6)] (7). One of the key features of complex 5 is the presence of an unusual pentacoordinated sulfido ligand(μ5-S). All the complexes have been characterized by multinuclear NMR, mass spectrometry and their structural architectures have been unambiguously established by single-crystal X-ray diffraction studies. In addition, theoretical investigations provided valuable insights into the electronic structures and bonding of these clusters.
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vendredi 4 octobre 2024
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Dates et versions

hal-04570828 , version 1 (20-06-2024)

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Subhash Bairagi, Debipada Chatterjee, Aishee De, Marie Cordier, Thierry Roisnel, et al.. Syntheses, Structures, and Bonding of Boron Containing Niobium and Ruthenium Clusters Stabilized by Chalcogens. Journal of Organometallic Chemistry, 2024, 1012, pp.123126. ⟨10.1016/j.jorganchem.2024.123126⟩. ⟨hal-04570828⟩
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