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Closed Access item Synthesis and Reactions of Manganese(II) Dialkyl Complexes Containing Monodentate and Bidentate Nitrogen Ligands

Authors:Cámpora, Juan
Palma Ramírez, Pilar
Pérez, Carmen M.
Rodríguez-Delgado, Antonio
Álvarez, Eleuterio
Gutiérrez-Puebla, Enrique
Keywords:Manganese, Dialkyl complexes, Metal alkyls, NMR
Issue Date:16-Jun-2010
Publisher:American Chemical Society
Citation:Organometallics 29(13): 2960-2970 (2010)
Abstract:In this paper we describe the synthesis of Mn(II) dialkyl compounds and their adducts with THF and pyridine. These compounds are useful precursors for the preparation of Mn complexes relevant to catalysis, such as dialkylmanganese(II) derivatives containing chelating nitrogen ligands. In contrast with previously known manganese(II) dialkyls, dibenzylmanganese can not be prepared from MnCl2 and benzylmanganese chloride due to the formation of insoluble mixed manganese−magnesium compounds. Homoleptic manganese(II) dialkyls are highly sensitive and often quite insoluble owing to their polymeric structure. However, adducts of type MnR2L or MnR2L2 (L = THF, pyridine) are soluble in hydrocarbon solvents and more readily isolated and stored than the homoleptic alkyls compounds. Manganese dialkyls as well as their THF or pyridine adducts react instantly with 2,2′-bipyridyl to afford the corresponding MnR2(bipy) complexes. Thus, the stabilized dialkylmanganese(II) THF or Py adducts represent a practical alternative to the more reactive but less easily handled homoleptic dialkyl precursors for synthetic purposes. In addition, the reactivity of MnR2(bipy) derivatives with O2 and the protic acid [H(OEt2)][BAr′4] (Ar′ = 3,5-C6H3(CF3)2) are described. The former reaction leads to the formation of a mixed-valence Mn(II)/Mn(III) alkyl complex containing a tetranuclear [Mn4O2] core.
Description:11 páginas, 8 figuras, 2 tablas, 4 esquemas.
Publisher version (URL):http://dx.doi.org/10.1021/om100190g
URI:http://hdl.handle.net/10261/37663
ISSN:0276-7333
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