Abstract
The first carbonyl free mixed valence cobalt(I)/cobalt(II) compound [2{L2Co(I)(η(6)-C7H8)}](2+) [Co(II)2Cl6](2-) (1) [L = PhC(N(t)Bu)2SiCl] was obtained by the reaction of four equivalents of anhydrous CoCl2 with five equivalents of N-heterocyclic chlorosilylene L. In contrast, the reaction of L with CoBr2 yielded [L2CoBr2] (2). Compound 1 was formed by the cleavage of Co-Cl bonds, the reduction of Co(II) to Co(I) and by the coordination of a toluene molecule. The chlorosilylene (L) functions as a reducing agent as well as a neutral σ-donor ligand. The toluene molecule coordinates to the Co(I) atom in an η(6)-fashion.
Highlights
The first carbonyl free mixed valence cobalt(I)/cobalt(II) compound [2{L2Co(I)(η6-C7H8)}]2+ [Co(II)2Cl6]2− (1) [L = PhC(NtBu)2SiCl] was obtained by the reaction of four equivalents of anhydrous CoCl2 with five equivalents of N-heterocyclic chlorosilylene L
Compound 1 was formed by the cleavage of Co–Cl bonds, the reduction of Co(II) to Co(I) and by the coordination of a toluene molecule
Compound 1 was obtained in a one pot synthesis of chlorosilylene L with anhydrous CoCl2 (Scheme 1)
Summary
A striking example is the isolation of the mixed valence cobalt(I/II) compound [(IPr·SiCl2)2Co(CO)3]+– [CoCl3(THF)]− on reaction of Co2(CO)[8] with IPr·SiCl2.7a Carbonyl free complexes with low-valent 3d transition metals are scarce but show interesting applications in the activation of small molecules and as enzyme mimics.[2] Among the first row transition metal complexes, some carbonyl free cobalt(I) complexes have been prepared using sterically crowded monodentate or chelating di-, tri-, or poly-dentate ligands Such complexes have been prepared by the reduction of Co(II) halides using alkali metals (e.g., KC8) as reducing agents.[10] In continuation of our ongoing research work to develop safer and more convenient synthetic methods for compounds with
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