“Triple-Decker Sandwich” Containing Planar {B2E2Pd} Ring (E = S or Se)

Joseph, Benson ; Prakash, Rini ; Bag, Ranjit ; Ghosh, Sundargopal (2020) “Triple-Decker Sandwich” Containing Planar {B2E2Pd} Ring (E = S or Se) Inorganic Chemistry, 59 (22). pp. 16272-16280. ISSN 0020-1669

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Official URL: http://doi.org/10.1021/acs.inorgchem.0c02062

Related URL: http://dx.doi.org/10.1021/acs.inorgchem.0c02062


In an effort to generate triple-decker complexes comprising a {PdCl2}moiety in the middle deck, we have explored the reactivity of [(Cp*M)2{μ-B2H2E2}], 1–4 (1: M = Co, E = S; 2: M = Co, E = Se; 3: M = Rh, E = Se; and 4: M = Ir, E = Se; Cp* = η5-C5Me5), with [PdCl2(COD)] (COD = 1,5-cyclooctadiene). The reactions led to the formation of a series of trinuclear heterometallic triple-decker complexes, [(Cp*M)2{μ-B2H2E2Pd(Cl)2}], 5–8 (5: M = Co, E = S; 6: M = Co, E = Se; 7: M = Rh, E = Se; and 8: M = Ir, E = Se). Formation of the complexes 5–8 occurred almost instinctively as a single product with the elimination of the COD ligand. These complexes are examples of novel triple-decker species having a planar bridging palladacycle ligand, in which the Pd metal exists as Pd(II) in an uncommon pseudo-octahedral environment with an elongated M–Pd bonding interaction. The new species, 5–8, have been characterized spectroscopically, and the structures of 5–7 were confirmed by single-crystal X-ray diffraction studies. The structure and bonding of these molecules were further analyzed with the help of density functional theory studies that found a strong electron donation from the B2E2 (E = S or Se) fragment of the middle ring to the axial metals, while a weak bonding interaction between group 9 metals and Pd.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:123770
Deposited On:13 Oct 2021 07:40
Last Modified:13 Oct 2021 07:40

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