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Article Dans Une Revue Journal of Organometallic Chemistry Année : 2023

Triple-decker complexes comprising heterocyclic middle-deck with coinage metals

Résumé

Earlier accounts of triple-decker complexes comprising main group elements and transition metals in the middle-deck, motivated us to synthesize triple-decker complexes containing coinage metals in the middle-deck. As a result, we have explored the reactivity of open-cage nido - [(Cp *M) 2 { mu-B 2 H 2 E 2 }], 1 -3 (Cp * = eta 5 -C 5 Me 5 , 1 : M = Co, E = S ; 2 : M = Co, E = Se; 3 : M = Rh, E = Se) with [CuBr(SMe 2 )]. All the reactions yielded triple-decker complexes, [(Cp *M) 2 { mu-B 2 H 2 E 2 CuBr}], 4 -6 ( 4 : M = Co, E = S ; 5 : M = Co, E = Se; 6 : M = Rh, E = Se) having [CuBr] in the middle-deck. The removal of the SMe 2 ligand resulted in the formation of complexes 4 -6 as a single product. These complexes are examples of triple-decker species having a planar 5-membered [B 2 E 2 Cu] (E = S or Se) middle deck, in which the Cu exists as Cu(I) with an elongated M-Cu bonding interaction. Synthesized complexes have been established by ESI-MS, multinuclear nuclear magnetic resonance (NMR), and IR spectroscopy. The solid-state structures of 5 and 6 were confirmed by single-crystal X-ray diffraction analyses. Density functional theory (DFT) analyses of these complexes have presented a high electron donation from the [B 2 E 2 ] (E = S or Se) fragment of the middle ring to the axial metals and a weak bonding interaction between group 9 metals and Cu.
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Dates et versions

hal-04057535 , version 1 (15-05-2023)

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Paternité - Pas d'utilisation commerciale

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Chandan Nandi, Ranjit Bag, Soumen Giri, Arindam Roy, Marie Cordier, et al.. Triple-decker complexes comprising heterocyclic middle-deck with coinage metals. Journal of Organometallic Chemistry, 2023, 990, pp.122667. ⟨10.1016/j.jorganchem.2023.122667⟩. ⟨hal-04057535⟩
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