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A combined experimental and theoretical study of bimetallic bis- And tris-homocubane analogues
, Joseph B., Prakash R., Pathak K., Roisnel T., Kahlal S., Halet J.-F.
Published in Royal Society of Chemistry (RSC)
2020
Volume: 44
   
Issue: 3
Pages: 674 - 683
Abstract
Synthesis of various metal-incorporated bis- and tris-homocubane analogues has been reported. Room temperature reactions of [Cp∗MCl2]2 (Cp∗ = η5-C5Me5, M = Ir or Rh) with chalcogenated borohydride reagents, Li[BH2E3] (E = S or Se), yielded a series of bimetallic bis- and tris-homocubane derivatives (1-7). The bishomocubane analogues belong to the 1,3-bishomocubane family with the general formula [(Cp∗M)2(μ-E)2(μ3-E)4(μ3-BH)2] (1: M = Ir, E = S; 2: M = Ir, E = Se; 5: M = Rh, E = S and 6: M = Rh, E = Se), and [(Cp∗Ir)2(μ-S)2(μ3-S)4(μ-BH2)2], 3, can be described as an unusual bishomocubane having two (μ-BH2) units with a missing-bond. In addition to these bishomocubanes, two trishomocubane derivatives [(Cp∗M)2(μ-E)3(μ3-E)4(μ3-BH)2] (4: M = Ir, E = S and 7: M = Rh, E = Se) were isolated from the above reactions. Trishomocubane 4 adopts a 1,2,4-trishomocubyl structure, whereas 7 is a D3-trishomocubyl analogue. In a similar fashion, thermolysis of [Cp∗CoCl]2 with Li[BH2E3] (E = S or Se) led to the formation of Co-1,3-bishomocubane analogues, [(Cp∗Co)2(μ-E)2(μ3-E)4(μ3-BH)2] (8: E = S and 9: E = Se). All the compounds were characterized by multinuclear NMR and IR spectroscopies and mass spectrometric analysis. The core geometries of 1-4 and 8 were unequivocally established by single-crystal X-ray diffraction studies. Density functional theory (DFT) computations further demonstrated that metals and chalcogen atoms play an important role in determining the thermodynamic stability of the bis- and tris-homocubane species. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
About the journal
JournalData powered by TypesetNew Journal of Chemistry
PublisherData powered by TypesetRoyal Society of Chemistry (RSC)
Open AccessNo